Etd

ABSTRACT
HUTCHINSON, SHAWN ROBERT. Thermoplastic polyacrylonitrile: investigation
of polymer structure, melt behavior and fiber properties. (Under the direction of
W. OXENHAM, B.S. GUPTA and A.E. TONELLI).
The objective of this research is to understand the structure, melt
behavior, and fiber properties of Amlon® D, part of a family of thermoplastic high
acrylonitrile (PAN) copolymer resins. A proposed crystal morphology model
based on predicted and observed comonomer sequence lengths and melting
behavior is presented. Thermograms of basic melt behavior demonstrate there
is melting, but surprisingly no evidence of a first-order phase transition is
observed.
Time-temperature stability and flow behavior was used to gain an
understanding of processing parameters. Thermogravimetric analysis with mass
spectrometry was used to study the stability. A capillary rheometer was used to
obtain detailed rheology data employing a range of die sizes, melt times and
shear rates.
Monofilaments were extruded using a single bore device with a range of
spin draw and draw ratios. Fiber tenacity and elongation were measured to
assess the efficacy of processing conditions. The solid state behavior of the
polymer is characterized and correlated with the mechanical properties using
wide angle x-ray diffraction and differential scanning calorimetry analyses.

THERMOPLASTIC POLYACRYLONITRILE
by
SHAWN ROBERT HUTCHINSON
A thesis submitted to the Graduate Faculty of
North Carolina State University
In partial fulfillment of the
Requirements for the degree of
Master of Science
TEXTILES
COLLEGE OF TEXTILES
Raleigh, NC
2005
Approved by:
_____________________________ _____________________________
_____________________________ _____________________________
Chairman of the Advisory Committee Co-Chairman of the Advisory Committee
ii
DEDICATION
This work is dedicated to
my parents,
sister,
family and
friends,
whose support made with work possible.
Thermoplastic Polyacrylonitriles
iii
THE ROAD NOT TAKEN
By Robert Frost
TWO roads diverged in a yellow wood,
And sorry I could not travel both
And be one traveler, long I stood
And looked down one as far as I could
To where it bent in the undergrowth; 5
Then took the other, as just as fair,
And having perhaps the better claim,
Because it was grassy and wanted wear;
Though as for that the passing there
Had worn them really about the same, 10
And both that morning equally lay
In leaves no step had trodden black.
Oh, I kept the first for another day!
Yet knowing how way leads on to way,
I doubted if I should ever come back. 15
I shall be telling this with a sigh
Somewhere ages and ages hence:
Two roads diverged in a wood, and I—
I took the one less traveled by,
And that has made all the difference. 20
Thermoplastic Polyacrylonitrile
iv
AUTOBIOGRAPHY
Shawn Robert Hutchinson was born on February 2, 1978 in Frankfurt am
Main, Hessen, Germany. Childhood was spent along the banks of the Ohio
River in Vienna, West Virginia collecting Native American artifacts and cultivating
towering gardens. In 1996, he graduated from Fuquay-Varina Senior High
School Salutatorian and Student Body President. After graduating cum laude
from Duke University with a B.A. in Computer Science and German minor, he
worked as a software developer with a dotcom in Washington, D.C. and New
York, NY.
Seeking to fulfill questions about the nature of existence, he sought an
experiential worship that was rediscovered in creativity – ultimately finding
Vedanta and Santhana Dharma as a profound system of self-knowledge. After a
period with the Sivananda Yoga Vedanta Center and travels in India, he returned
to graduate school at North Carolina State University to complete the
development of a new fabric. Unbeknownst to him lie waiting the world of
polymers and fibers. How thankful he is to have these human experiences and
hopes to utilize his skills most effectively in improving the human condition.
v
ACKNOWLEDGEMENTS
The author would like to express his sincere appreciation to the committee
chairpersons Drs. W. Oxenham and B.S. Gupta. Their support, motivation and
suggestions made this project possible. Dr. Gupta, especially, provided indelible
guidance on the ethics of scientific inquiry. Candid debates with Dr. A.E. Tonelli
provided insight into the structure and properties of polymers and inspiration for
an aspiring scientist. Appreciation is also extended to members Drs. J.P.
Hinestroza and D.A. Shiffler. Many discussions with technical advisor C. Moses,
of the Institute of Textile Technology provided enduring encouragement and
support. Without hesitation, Dr. K.R. Beck invested his time into teaching
analytical techniques and skills. Drs. S.M. Hudson and R. Kotek provided key
recommendations along the journey.
Eine hertzliche Bedanken für Birgit Anderson and Ted Dodson, whose
technical assistance made this project possible. Jason Dinsmore and Sabapathy
Sankar of the Chemistry Department at North Carolina State University provided
nuclear magnetic resonance training. Tulane University, Drs. D. De Kee, Y.
Zhong, W. Liu, and the Tulane Institute for Macromolecular Engineering and
Science (TIMES) graciously allowed their equipment to be used for the
rheometry and part of the thermogravimetric analysis work. Thanks to Dralon,
GmbH for allowing their fibers to be the subject of investigation free of charge.
This work was sponsored by the Master’s Graduate Fellowship Research
Program from the Institute of Textile Technology. The financial support of the
member companies is greatly appreciated.
vi
TABLE OF CONTENTS
LIST OF TABLES............................................................................................... IX
LIST OF FIGURES .............................................................................................. X
0 INTRODUCTION ...............................................................................................1
1 ACRYLIC CHEMISTRY.....................................................................................3
1.1 ACRYLIC MONOMERS......................................................................................4
1.2 MONOMER SYNTHESIS ...................................................................................5
1.3 POLYMERIZATION ...........................................................................................7
1.3.1 Bulk Polymerization .........................................................................7
1.3.2 Solution Polymerization ...................................................................8
1.3.3 Heterogeneous (Emulsion & Suspension) Polymerization ..............9
2 POLYACRYLONITRILE FIBER TECHNOLOGY ............................................10
2.1 HIGH ACRYLICS & MODACRYLICS .................................................................10
2.2 BICOMPONENT FIBERS & CRIMP ...................................................................12
2.3 DYEABILITY .................................................................................................14
2.3.1 Acid & Base Dyes..........................................................................14
2.3.2 Producer Dyed ..............................................................................14
2.3.3 Pigmented .....................................................................................15
2.4 TECHNICAL APPLICATIONS ...........................................................................16
2.4.1 Reinforcing Fiber (Asbestos Replacement) ...................................16
2.4.2 Carbon Fibers................................................................................16
2.4.3 Moisture Absorbent Fibers ............................................................17
3 FIBER SPINNING TECHNOLOGY..................................................................18
3.1 WET SPINNING ............................................................................................19
3.1.1 Process .........................................................................................19
3.1.2 Solvents.........................................................................................19
3.1.3 Polymer .........................................................................................20
3.1.4 Coagulation ...................................................................................20
3.1.5 After treatment...............................................................................21
3.2 DRY SPINNING .............................................................................................23
3.2.1 Process .........................................................................................23
3.2.2 Solvents.........................................................................................24
3.2.3 Polymer .........................................................................................24
3.2.4 Evaporation & Cross Sectional Shape...........................................25
3.2.5 After treatment...............................................................................25
3.3 MELT SPINNING ...........................................................................................27
3.3.1 Conventional Thermoplastics Processing......................................27
3.3.2 Imparted melt processability..........................................................28
3.3.3 PAN Hydrates................................................................................29
3.3.4 Summary of Prior Art in ‘Melt Processable’ PANs .........................29
vii
4 MARKETS AND POTENTIAL .........................................................................30

4.1 TRENDS IN THE WORLDWIDE SYNTHETIC FIBER PRODUCTION .........................30
4.2 TRENDS IN THE ACRYLIC FIBER MARKET .......................................................30
4.2.1 Markets in the United States .........................................................32
4.2.2 Markets in Europe and Asia ..........................................................39
4.2.3 Market Prospects...........................................................................39
4.3 COST ANALYSES .........................................................................................40
4.3.1 Poly(ethylene terephthalate)..........................................................40
4.3.2 Poly(propylene) .............................................................................41
4.3.3 Poly(amides) .................................................................................41
4.3.4 Solution processable high acrylonitrile copolymers .......................42
4.3.5 Melt processable high acrylonitrile copolymers .............................43
4.4 POTENTIAL APPLICATIONS FOR THERMOPLASTIC PAN ....................................48
4.4.1 Comparative properties between synthetic fibers..........................48
4.4.2 Deniers, profiles and multicomponent fibers..................................49
4.4.3 Reinforcing fiber ............................................................................50
4.4.4 Carbon fibers.................................................................................50
4.4.5 Composite and carbon carbon composite components.................52
4.4.6 Limitations from the hot-wet conundrum........................................53
4.4.7 Outdoor fabrics ..............................................................................54
4.4.8 Nonwovens....................................................................................54
4.4.9 Membranes, Films and Conductivities...........................................54
5 POLYMER MICROSTRUCTURE ....................................................................57
5.1 EXPERIMENTAL ............................................................................................61
5.1.1 Materials........................................................................................61
5.1.2 Solution 13C Nuclear Magnetic Resonance ...................................62
5.1.3 Differential Scanning Calorimetry ..................................................63
5.2 RESULTS AND DISCUSSION ...........................................................................63
5.2.1 Solution 13C Nuclear Magnetic Resonance ...................................63
5.2.2 Differential Scanning Calorimetry ..................................................70
5.2.3 Conclusions...................................................................................72
6 POLYMER THERMOMECHANICAL ANALYSES ..........................................76
6.1 EXPERIMENTAL ............................................................................................77
6.1.1 Drying ............................................................................................77
6.1.2 Fourier Transform Infrared Spectroscopy......................................77
6.1.3 Thermal Gravimetric Analysis & Mass Spectrometry.....................78
6.1.4 Capillary Rheometry ......................................................................78
6.2 RESULTS AND DISCUSSION ...........................................................................81
6.2.1 Vacuum Drying ..............................................................................81
6.2.2 Chemical Composition...................................................................81
6.2.3 Thermal Stability............................................................................83
6.2.4 Degradation Byproducts ................................................................85
6.2.5 Melt Time.......................................................................................86
6.2.6 Capillary Rheometry ......................................................................90
viii
6.2.7 Conclusions...................................................................................91
7 MELT EXTRUSION .....................................................................................95
7.1 EXPERIMENTAL .......................................................................................98
7.1.1 Extrusion Device .........................................................................98
7.1.2 Mechanical Properties .................................................................102
7.1.3 Size Exclusion Chromatography .................................................102
7.1.4 Wide Angle X-ray Diffraction .......................................................102
7.1.5 Differential Scanning Calorimetry ................................................103
7.2 RESULTS & DISCUSSION ............................................................................103
7.2.1 Melt Spinning...............................................................................103
7.2.2 Mechanical Properties .................................................................105
7.2.3 Molecular Weight.........................................................................107
7.2.4 Wide Angle X-ray Diffraction .......................................................119
7.2.4.1 Background ...............................................................................119
7.2.4.2 Results and Discussion .............................................................121
7.2.5 Paracrystallinity ...........................................................................127
7.2.6 Conclusions.................................................................................131
8 GENERAL CONCLUSIONS ..........................................................................132
8.1 FUTURE WORK ..........................................................................................133
9 LITERATURE CITED ....................................................................................134
ix
LIST OF TABLES
Table 1. Raw Materials and Conversion Costs for Major Thermoplastic Polymers
.....................................................................................................................44
Table 2. Comparative Properties of Synthetic Fibers..........................................49
Table 3. Comonomer Distributions and Number Average Sequence Lengths for
Methyl Acrylate and Vinyl Acetate Copolymers ...........................................67
Table 4. Thermogram Inflection Points and Enthalpies for Dried and Undried
Amlon® D Pellets .........................................................................................73
Table 5. Capillary Rheometry: Die Dimensions and Shear Rates......................79
Table 6. Extrusion Conditions: Melt Temperature and Melt Times ....................80
Table 7. Power Law Index for Dried Amlon® D Capillary Rheometry ..................90
Table 8. Melt Extrusion, Winding and Drawing Conditions ...............................100
Table 9. Tenacity and Elongation for Meltspun Amlon® D Fibers by Total
Effective Draw Ratio ..................................................................................104
Table 10. Size Exclusion Chromatography Retention Times for Amlon® D Fibers
...................................................................................................................108
Table 11. Wide Angle X-Ray Diffraction Reflection Spectrum Analysis of Amlon®
D Fibers .....................................................................................................123
Table 12. Differential Scanning Calorimetry Data for Amlon® D Fiber ..............128
x
LIST OF FIGURES
Figure 1. Poly(acrylonitrile-co-methyl acrylate) ...................................................11
Figure 2. Synthetic Fibers Market: Acrylics, Polyester, .......................................31
Figure 3. Capacity, Production, Domestic Shipments, Imports, Exports and
Consumption in United States Acrylic Fiber Market.....................................33
Figure 4. Capacity, Production and Consumption in the Acrylic Fiber Markets by
Major Geographical Regions .......................................................................34
Figure 5. Acrylic Fiber Consumption by Apparel, Home .....................................36
Figure 6. Synthetic Fibers Market: Acrylics, Polyester, .......................................38
Figure 7. Raw Material, Intermediary and Fiber Costs for Poly(ethylene
terephthalate), Poly(propylene), Poly(amides) and Polyacrylonitriles. .........46
Figure 8. Solution 13C NMR Spectra of Amlon® D in d6-DMSO...........................68
Figure 9. Number Average Acrylonitrile Sequence Length for Methyl Acrylate
Copolymers by Mole Fraction of Acrylonitrile: Observed Lengths and Zero-
Order, First-Order, and Second-Order Markov Models Lengths ..................69
Figure 10. Differential Scanning Calorimetry Cooling Thermograms for
Poly(ethylene terephthalate) Tire Cord Fibers .............................................72
Figure 11. Differential Scanning Calorimetry Thermograms for ..........................74
Figure 12. Weight Loss during Vacuum Drying of Amlon® D Pellets...................82
Figure 13. Fourier Transform Infrared Spectra of Amlon® D Pellets ...................82
Figure 14. Quasi-Isothermal Stability Thermogravimetric Analyses....................84
Figure 15. Isorate Degradation Thermogravimetric Analyses .............................84
xi
Figure 16. Mass Spectrometry Fragments of Undried Amlon® D Pellets Collected
with Tandem Isothermal Thermogravimetric Analyses. ...............................87
Figure 17. Melt fractures of Dried Amlon® D Extrudate.......................................92
Figure 18. True Viscosities by True Shear Rate for Dried and Undried Amlon® D
and Polypropylene by Temperature and Melt Time .....................................93
Figure 19. Melt Extrusion Device with Detail of Bore and Shroud Setup ..........101
Figure 20. Linear Density (denier) of Melt-spun Amlon® D Fiber ......................109
Figure 21. Load by Elongation Curves for Amlon® D Fiber, Plastic Deformation
and Deformation Strengthening .................................................................110
Figure 22. Tenacity for Amlon® D Fiber by Total Effective Draw Ratio .............111
Figure 23. Elongations for Amlon® D Fiber .......................................................112
Figure 24. Tenacity by Elongation and Spin Draw Ratio for Amlon® D Fiber ....113
Figure 25. Tenacities by Draw Ratio for Amlon® D Fiber ..................................114
Figure 26. Elongations at Break for Amlon® D Fiber .........................................116
Figure 27. Elongation at Break for Amlon® D Fiber...........................................117
Figure 28. Wide Angle X-Ray Diffraction Reflection Spectrum for Fibers Extruded
with a Heat Shroud. ...................................................................................124
Figure 29. Wide Angle X-Ray Diffraction Transmission Patterns for Fibers
Extruded with a Heat Shroud .....................................................................125
Figure 30. Second Cooling Enthalpies for Amlon® D Fiber ...............................129
1
0 Introduction
The ability to precisely control the physical structure of materials
profoundly affects their properties. This ability will be one of the defining features
of the new century. Acrylic is a unique example.
The commercial history of polyacrylonitrile dates back to the 1950s when
Bayer and DuPont patented dry spinning technologies. The polymer degraded
before melting, which rendered it processable only in harsh, toxic solutions.
Inherent ultraviolet (UV) and chemical resistances made the fibers special in a
number of applications and, combined with its high resiliency, a fiber of choice as
a wool substitute at that time. However, low throughputs and expensive solvent
recovery associated with solution processing made the fibers expensive.
Variations in fiber diameter and surface imparted from solution processing, as
well as competition from nylon, limited the success of the fiber. Lack of melt
processability prevented the polymer from reaching its full potential in all
contemporary thermoplastic polymer applications.
For decades, scientists sought ways to melt-process polyacrylonitrile,
because of low conversion costs and potential mechanical property
enhancements. Numerous attempts were made to impart melt-processability,
but few, if any, met commercial success. Finally, in the 1990s, British Petroleum
(BP) developed and patented a polymerization reaction that created a family of
the first innately thermoplastic high acrylonitrile copolymers under the trade name
Amlon®. BP claims that under extremely low feed rates, the composition of a
copolymer can be controlled sufficiently to impart melt processability. Thus,
2
acrylic can now be processed in an environmentally friendly manner without the
aid of solvents. However, little is publicly known about how to process this
polymer. Generating such data and investigating the structure-property
relationship of resulting fibers is essentially the focus of this study.
The objective of this thesis is to first present an economic picture of the
U.S. and worldwide acrylic fiber market, synthetic fiber market, and raw material
costs. Potential applications including fibers, films, fabrics and composites are
explored. Secondly, the basic polymer science in terms of copolymer structure
and crystal morphology is investigated to understand how polyacrylonitrile can be
made melt processable. Next, melt behavior, stability and rheology are studied
to determine optimal processing conditions. Finally, fibers were melt-extruded
and correlations were made between extrusion conditions, microstructure and
mechanical properties.
Acrylic Chemistry 3
1 Acrylic Chemistry
Vinyl monomers comprise a vast majority of modern synthetic chemicals.
Acrylic is a constituent of a well-known subset of Acrylic Butadeine Styrene
(ABS) plastics. ABS materials include some of the most specialized and highly
valued of all petrochemicals. In particular, their chemical, thermal and ultraviolet
(UV) resistances enable them to satisfy a technical niche all their own. Even
amongst apparel markets, acrylonitrile provides an important alternative to
woolens. ABS polymer applications affect nearly every level of daily human
existence.
Polyacrylonitrile (PAN) and its copolymers are the only ABS polymers
used today in fiber applications because it is sufficiently paracrystalline, which
gives it the mechanical stability necessary for applications. The acrylonitrile
sidegroups impart unique resistances and the strong interactions between them
traditionally prevent the material from melting before it degrades. At
temperatures above 200ºC, chemical changes begin to occur as the sidegroups
begin to crosslink and cyclize. On one hand, PAN has desirable properties that
are not found in other commodity fiber forming polymers such as polyamide,
polypropylene and polyethylene terephthalate. However, these properties also
prevent the polymer from being used in more general consumer plastic
applications such as films because of processing requirements.
In the 1950s companies like DuPont and Bayer developed the first
specialized systems to process PAN in solution. Yet, the environmental and
economic constraints from harsh solvents and low throughputs limited the
Acrylic Chemistry 4
commercial success of PAN applications. The nature of the required processing
equipment itself restricted most of the uses to fibers. Accordingly, many
scientists and chemical companies attempted to alter the chemical behavior so
as to impart melt processability. To date, however, none of the techniques have
proven successful on a mass scale due to pervading deficiencies in the
mechanical properties of products and the economics of their production.
1.1 Acrylic monomers
‘Acrylic’ is the colloquial term for polyacrylonitrile, or PAN, and its
copolymers. However, in organic chemistry, ‘acrylic’ applies to a classification of
vinyl monomers having the basic form, where R1 and R2 are sidegroups:
H R1
C C
H C O
O R2
The most widely used forms of acrylics are:
• CH2=CH⎯COOH, arylic acid
• CH2=CHCH3⎯COOH, methacrylic acid
• CH2=CH⎯COO⎯CH3, methyl acrylate
• CH2=CCH3⎯COO⎯CH3, methyl methacrylate (Plexiglas®)
• CH2=CH⎯CO⎯NH2, acrylamide
• CH2=CH⎯CHO, acrolein
• CH2=CH⎯CN, acrylonitrile (AN)
Acrylic Chemistry 5
Other side groups in place of the R1 and R2, such as halides, enable a variety of
property enhancements including flame resistance and dyeability.
In particular, methyl methacrylate is one of the mostly commonly used
acrylic monomers due to their aging resistance. With a relatively easy bulk
polymerization process, this monomer lends itself well to molding and casting at
low temperatures, from 45 to 90 °C. In bulk, the liquid polymer requires curing
from 1.25 to 2.5 hours ranging in temperature from 250 to 315 °C.
Cast methyl methacrylate is available in a variety of shapes – generally
sheets, rods and tubes. The properties of these thermoplastic acrylics come in
three grades: 1) outdoor use where moderate transparency is required having
half the weight and tenfold impact resistance of glass, 2) heat-resistant that
resists crazing and solvents, and 3) technical applications where high optical
clarity and low defects are required. Cast materials are available in a variety of
sizes with auxiliary properties from colors to scratch resistance [2].
1.2 Monomer Synthesis
Most acrylic monomers are synthesized through an initial reaction of
hydrogen cyanide (HCN). Originally, methyl methacrylate was synthesized with
acetone and hydrogen cyanide. Later, ethylene oxide replaced acetone. Other
processes that form higher acrylates are alcoholysis or transesterification.
Catalysts such as toluene-sulfonic acid are used to increase yields. Inhibitors
such as hydroquinone are often used to prevent spontaneous polymerization.
Acrylic Chemistry 6
Aside from being the raw material for the polymerization of PAN,
acrylonitrile is often also used as a precursor for high acrylic esters. The three
main means of synthesizing acrylonitrile are 1) from propylene, ammonia and
oxygen, 2) the dehydration of ethylene cyanohydrin into acrylonitrile and water
with a catalyst and 3) a reaction of acetylene and HCN at high temperature with a
catalyst, usually nickel carbonyl and hydrochloric acid:
1) 4CH2=C=CH2 + 4NH3 + 5O2 ⎯⎯⎯→ 4CH2=CH⎯CN + 10H2O

catalyst
2) OH⎯CH2⎯CH2⎯CN ⎯⎯⎯→ CH2=CH⎯CN + H20

catalyst
400−500o C
3) C2H2 + HCN ⎯⎯⎯⎯→ CH2=CH⎯CN
catalyst
The hydrolysis of acrylonitrile and methacrylonitrile is also used to synthesize
acrylic acid and methacrylic acid:
H+
CH2=CH⎯CN + H2O ⎯⎯→ CH2=CH⎯COOH + NH3
In general, most acrylic monomers are synthesized with a catalyst directly from
HCN or indirectly through acrylonitrile. Regardless, the reactions involve
explosive combinations of high temperatures, high pressures and large volumes
of cyanides. Thus, extreme care is required when handling the reactions and
monomers [2].
Acrylic Chemistry 7
1.3 Polymerization
The two sidegroups, R1 and R2, provide the means for a wide array of
constituent compounds. Polymerization occurs between the double-bonded
carbon atoms and creates high molecular weight polymers. The degree of
polymerization and average molecular weight can create significant phase
differences at room temperatures ranging from an oily liquid to a brittle solid.
Most acrylic bulk polymers are thermoplastic, or they soften at a specific
temperature. Thermosetting, or crosslinking polymer chains, can decrease and
altogether vanquish the plasticity of the polymer. Dimethacrylates and diallylic
compounds are often used as thermosetting agents. Partially crosslinked
polymers can yield desirable properties such as better heat resistance while
retaining the plastic nature [2].
As in the synthesis of the monomer, polymerization is often a highly
exothermic reaction. Control of the reaction and temperature are highly coupled.
Polymerization of acrylics usually occurs in three ways: 1) bulk, 2) solution and
3) heterogeneous systems.
1.3.1 Bulk Polymerization
Bulk polymerization takes place directly on the monomer with the aid of a
soluble catalyst and is used for most cast materials. The polymer melt is allowed
to pre-polymerize to about 10% before it is poured into the mold. The mold is
subjected to low temperatures, allowing the reaction to continue until the rate
significantly decreases. At this point, the temperature is increased to the boiling
Acrylic Chemistry 8
point of the monomer to complete the reaction. This method is used primarily for
2-dimensional molds. Autoclaves are used for bulkier dimensions. The high
molecular weight products are rigid and resistant to solvents.
1.3.2 Solution Polymerization
Lower molecular weight polymers are synthesized through solution
polymerization. In this variation, the monomer and catalyst are added to a
solvent in which both the monomer and polymer are soluble. Ethyl acetate,
toluene and acetone are favorable solvents. As a result, this method is useful
when the end product contains both solvents and the acrylic polymer, such as
lacquer, some adhesives and most water-resistant films. The molecular weight is
controlled by the amount of catalyst, ratio of solvent to monomer and reaction
temperature [2].
Solution polymerization is used by many of the PAN fiber producers as a
means of synthesizing the polymer in a form that is easily solution-spun because
the polymer is already in a spinning solution. Materials having as little as 50%
acrylonitrile by weight can be synthesize by this method. For vinyl compounds,
dimethylformamide is usually the solvent. A range of patents to various chemical
companies in the 1960s-1970s outlined a variety of initiators, catalysts, and
processes [3].
Acrylic Chemistry 9
1.3.3 Heterogeneous (Emulsion & Suspension) Polymerization
Of the heterogeneous polymerization mechanisms, emulsion and
suspension occupy the vast majority of preferred methods. For emulsion, an
emulsifier and catalyst are dissolved in water. The monomer and surfactant are
added to this mixture and agitated. A variety of emulsifiers and surfactants yield
myriad reactions. The surfactant is arguably the most important part of the
system as it is responsible, at sequential stages, first as a dispersant, second as
a protective material to prevent coagulation and finally to suspend the solid
polymer particles in water for a stable mixture.
Suspension polymerization reacts in a similar way to emulsion, yet the
monomer is dispersed into small droplets. A monomer-soluble catalyst is then
added. Thus, unlike the emulsion system where polymerization occurs in water,
suspension polymerization occurs in the monomer droplets. After the reaction is
complete, the water is drained and droplets are dried for further processing [2].
Polyacrylonitrile Fiber Technology 10
2 Polyacrylonitrile Fiber Technology
In the 1950s, DuPont created the first acrylonitrile fiber, Orlon®. It was a
dry-spun fiber composed of 100% acrylonitrile. This fiber had several defects
that led to the next stage in polymer engineering. In particular, the high polarity
of the acrylonitrile sidegroups and rigid conformation made solution processing
difficult. Post-spinning processes such as dyeing were also adversely affected.
As a result, copolymerization with vinyl or vinylidene compounds enabled the
structure to be opened and softened [4].
2.1 High Acrylics & Modacrylics
The degree of copolymer delineates two types of acrylonitrile compounds:
1) high acrylic fibers consisting of at least 85% acrylonitrile (AN) and 2) modified
acrylics (modacrylics) consisting of 35-85% acrylonitrile. Typical high acrylonitrile
comonomers include methyl methacrylate, vinyl acetate or methyl acrylate, the
latter is shown in Figure 1.
Flammability and ignition behavior of high acrylic and modacrylics are
similar to other synthetic fibers like nylon, polyester, olefins and wool. They tend
to melt and burn rather than char and burn as do cellulose fibers. Of the
synthetics, however, high acrylic has a Limiting Oxygen Index similar to cotton.
Both are considered relatively flammable. For applications where flammability is
key, such as carpets, sleepwear, draperies and bedding, fibers must be self-
extinguishing [5]. To pass flammability tests, halogen compounds such as vinyl
chloride, vinylidene chloride and vinyl bromide are used. Commercially, only the
halogen modacrylics provide sufficient flame resistance for any application other
than carpet. Nearly all flame retardant high acrylic production has ceased [6].
Due to the low boiling points of halogens, polymerization of modacrylics is
conducted under increased pressures. Vinyl chloride (VC) requires the highest
pressure and is relatively unreactive in copolymerization with acrylonitrile. Free
radical polymerization of polyvinyl chloride and acrylonitrile occurs relatively fast.
Copolymerization by means of adding an AN monomer to a VC-terminated chain
occurs quickly. However, adding a VC monomer to an acrylonitrile-terminated
chain occurs slowly. Thus, the concentration of AN is low. The free radical is
unlikely to react with the vinyl chloride monomer. Thus, the copolymerization
process requires excess VC and is controlled by the concentration of AN
monomer. This reaction is generally conducted in a batch process. Molecular
weight and separation of toxic unreacted monomer presents difficulties.
* CH2 CH n CH2 CH m *
C C O
O
N
CH3
Figure 1. Poly(acrylonitrile-co-methyl acrylate)
Unlike VC, copolymerization of vinylidene chloride is conducted at lower
pressures with a more balanced concentration to inclusion ratio. Vinyl bromide
has a similar reaction rate and reaction mechanism. However, bromide is
seldom used solely as a flame retardant. Generally, to create copolymers of
sufficient molecular weight for fibers, the reaction rate is limited by a required low
concentration of initiator [6].
Most modacrylics are wet-spun using solvents suitable for acrylonitrile.
Dynel® appears to be the only exception to this process as it is either dry-spun
with acetone or melt spun. During spinning, other compounds are added for
increased flame retardance (antimony oxides), light stabilizers (titanium dioxide)
and color stabilizers (pigments).
Wet spinning of modacrylics is conducted by a similar method to high
acrylics. However, as halogens are sensitive to heat, minimizing heat exposure
is critical during solution- and fiber-formation stages. During processing, small
amounts of HCl and HBr are evolved creating mildly corrosive acids. Either in
spinning or in customer processes, a weak base or epoxide is often added after
heating to reduce acidity.
Other comonomers are used to alter the behavior of acrylics. Acrylamide
is often used to control shrinkage and physical properties. Sulfonates improve
dyeability [6].
2.2 Bicomponent Fibers & Crimp
The class of bicomponent fibers come in many forms and can be spun
from either the melt or solution. To date, the only commercially available acrylic
bicomponent is a side-by-side composite, developed by DuPont. The
construction, due to the composition of the two components creates a crimp
similar to that observed in wool from the ortho- and para-cortexes. Belonging to
this group of crimped bicomponents are water-reversibles and irreversibles.
In 1958, DuPont introduced the only water-reversible (through drying)
Type 21 Orlon® bicomponent using hydrophobic PAN and a hydrophilic
copolymer of AN with a sulfonate monomer. Although the spinerette holes are
circular, a mushroom-shaped cross section is formed from forces in the gellation
process. PAN is the ‘cap’ and AN/sulfonate is the ‘stem.’ Type 21 Orlon® as
sold to the textile mill has primarily mechanical crimp. However, through
exposure to water in dyeing and drying, a spiral crimp can be developed. The
hydrophilic stem shrinks as water is removed. Uniquely, the properties of the
AN/sulfonate compound enable this swelling and contraction to occur repeatedly.
However, the mechanical forces providing the crimp are relatively low, so the
crimp response only occurs when the fabric is not hung or blocked.
Irreversible crimps can be constructed using a variety of copolymers. The
two types of copolymers can both contain high contents of acrylonitrile, a high
and modacrylic levels, or both modacrylics. Discontinued in 1990, DuPont’s
Type 24 Orlon® was an example of a dry-spun irreversible crimped bicomponent.
Wet-spun bicomponents are more difficult to assemble. Only two technologies
have emerged with various feed patterns. In either case, ensuring a consistent
cross section composition is difficult – ranging from 100% component A to 100%
component B with a sandwich construction in between. Non-water-reversible
bicomponent crimps are often used in blends with a monocomponent fiber where
bulk and hand are optimized [6].
2.3 Dyeability
2.3.1 Acid & Base Dyes
Dyeing acrylic with an acid was the original method of coloring fibers.
There were a number of drawbacks that prevented this from becoming the de
facto standard. First, the dye sites were based on weak bases such as 2-vinyl
pyridine. A strong acid was thus required in the bath to protonate the site and
make it dyeable. Second, the amine group reduced the heat stability of the fiber.
Further, the base color of the acid-dyeable fiber was cream and the fastness was
not noteworthy. Finally, cost of the monomer was prohibitive.
The introduction of basic (cationic) dyes by DuPont and Bayer in the
1950s, Sevron® and Astrazon® dyes respectively, relegated acid-dyeable fibers
to a specialty niche. The range of dyes was expanded as they had strong affinity
for the sulfonic and sulfatic dyesites introduced from the polymerization initiator.
Basic-dyeable fibers were less expensive as the monomer could be easily
recovered in distillation enabling a continuous dyeing range. Further, these
fibers had a whiter base and could be dyed at a more neutral pH with brilliant
colors having better fastness [6].
2.3.2 Producer Dyed
When considering total worldwide acrylic fiber production, producer-dyed
fibers occupy a small market share. However, in their application, they offer
substantial cost savings for more commodity colors. Dyeing in the production
stage occurs by three means: 1) gel state, 2) solution (dope) and 3) tow. During
wet spinning, acrylic fibers have a porous structure of at least 50% void volume
that is well suited for dyeing. Dye penetration is rapid and can be applied in
numerous stages – in coagulation, during washing and stretching or after
stretching. In contrast, dry-spun fibers have an insufficiently porous structure in
the gel state to facilitate producer-dyeing [6].
2.3.3 Pigmented
Among other characteristics, acrylics are lauded for their lightfastness.
This reputation can be maintained without sacrificing strength through pigments.
High acrylics tend to have better light fastness than modacrylics as the latter can
lose halogen groups upon exposure to heat and light. Further, hydrogenated
halogens become brittle and discolor due to induced nitrile polymerization. High
comonomer content also makes the fiber more permeable to oxygen. Oxygen
causes chain scission by reacting with weak bonds on the backbone forming
hydroperoxides.
Pigments are added into the spinning solution as a dispersion in a dilute
polymer solution. Individual suspensions or one suspension can be added. No
significant alteration to the spinning process is required [6].
2.4 Technical Applications
2.4.1 Reinforcing Fiber (Asbestos Replacement)
Asbestos fibers were well suited for mechanical reinforcement
applications. Documented health hazards spurred interest in identifying
alternatives. Important considerations include tenacity and modulus, retention of
modulus in warm-moist conditions, resistance to alkali degradation and ability of
the fiber to bond to cement. To acquire high tenacity over 70 cN·tex-1, high
molecular weight (100,000 to 500,000) and high orientation are required.
Modifying agents in modacrylics can significantly reduce the mechanical
performance of fibers. Gel spinning acrylic fiber has yielded molecular weights
over 1 million, but cost prohibits any commercial reinforcement applications [6].
2.4.2 Carbon Fibers
Acrylic fibers are a prominent precursor for carbon fiber, over rayon and
pitch, differing by their achievable properties. The fiber must be stabilized in
order to enable its conversion to a cyclic carbon structure. Typically, carboxylic
acids or vinyl bromide copolymers cause ionic initiation and both lower the
temperature for cyclization and moderate the exotherm. A more balanced
exotherm prevents heat buildup and charring in yarn bundles. Effective
monomers include acrylic acid, methacrylic acid, itaconic acid and vinyl bromide.
As in reinforcing fibers, having superior mechanical properties of the fiber
precursor is highly advantageous as it also generates stronger carbon fibers.
High molecular weights of over 1 million are sought. High orientation is also
required to enable the chains to contribute completely to the overall strength of
the fiber. All fiber spinning technologies are utilized with tradeoffs between
productivity and fiber denier [6].
2.4.3 Moisture Absorbent Fibers
In many applications, the comfort of a fiber is evaluated on its ability to
absorb moisture without feeling damp or to wick moisture away to an outer
surface where it is evaporated. Dunova® by Bayer was one of the first fibers to
enable this mechanism with a core of thousands of pores and channels with a
protective skin. It absorbs a nontrivial amount of water without feeling wet [6].
Fiber Spinning Technology 18
3 Fiber Spinning Technology
Traditionally, high acrylics and modacrylics are solution-spun using either
‘wet’ or ‘dry’ spinning conditions. The first form of solution-spun fibers appeared
in the mid 1850s with the wet spinning of cellulosics into Chardonnet silk. In this
process, after nitrating cellulose with a sulfuric acid/nitric acid solution, it was
dissolved in a solvent to form a viscous ‘dope.’ The gel was forced through a
spinneret forming fibers of cellulose nitrate. Afterwards, the fiber is washed,
stretched and denitrified in an ammonium hydrosulfide bath. This application
illustrates a general method of wet-spinning fibers – convert the fiber to a soluble
form, induce a phase separation to form the fibrous network, and apply an after
treatment to solidify to the desired structure. This process is still used today in
the manufacture of rayon [7].
Two other methods of solution spinning exist: 1) insoluble structures that
are formed after spinning via a reaction of soluble parts and 2) unchanged
soluble chemical forms. Formation of polyvinyl alcohol fibers is an example of
fiber reactant wet spinning. Traditional polyacrylonitrile represents the most
commercially significant (volumetrically) solvent-spun product. This is
accomplished in either a ‘wet’ or ‘dry’ condition. The unifying characteristic of all
solvent spinning systems is that the solvent is miscible in water. This facilitates
its easy removal after spinning [7].
3.1 Wet Spinning
Wet-spinning systems account for nearly 85% of the worldwide acrylic
fiber production. Many factors contribute to this dominance. A wide array of
solvents can be used, depending on raw material, polymer solubility, after
treatment and economics. The process is noted for its large production capacity
in a relatively safer human environment with low potential for human exposure.
Finally, the fiber in gel form is porous, allowing for in-line dyeing [8].
3.1.1 Process
In the wet-spinning process, dissolved polyacrylonitrile is pumped through
a spinneret that is submerged in a coagulating bath. The bath contains the
solvent and water. As the polymer solution passes through the coagulant or
nonsolvent, a phase change occurs whereby the solvent diffuses out and the
nonsolvent diffuses in. The newly formed fibers emerge in a gel form from the
bath where they are later subjected to a series of aftertreatments.
3.1.2 Solvents
The most commonly used solvents are dimethylformamide (DMF),
dimethylacetamide (DMAc), sodium thiocyanate, and nitric acid, occupying
approximately 24%, 24%, 20%, and 10% of production capacity, respectively [7].
Resulting fiber structures are determined by what solvent, polymer and coagulant
are used. These choices have corresponding options for after-treatment steps.
3.1.3 Polymer
Solution properties and practical considerations limit the polymer
concentrations. Polymer solubility and solution spinning pressure limits high
concentrations. The ability of a solvent to maintain a spinning solution without
gelation limits polymer solubility. Commercial systems tend to enhance gelation,
so the polymer concentration limit in DMF and DMAc is 30%. High molecular
weight and concentrations create high solution viscosity. Thus, equipment
design limits line speeds and coagulant temperature. However, too low
concentrations prevents proper coagulation and proves too costly for solvent
recovery [7].
3.1.4 Coagulation
Fiber differences from wet and dry spinning result from the stage where
the shape is formed – the coagulation bath. A wet spinneret uses from 20,000 to
100,000 capillaries ranging in diameter from 0.05 to 0.25 mm. Polymer content,
flow rate and temperature are the key parameters that control the product
behavior. Shortly after the emergence of the gelated structure from the
spinneret, physical chemistry mechanisms of heat transfer, mass transfer, fluid
mechanics and solution thermodynamics govern the phase transition as the dope
stream becomes the fiber precursor. In particular, solution and bath temperature
affect the rate of heat transfer, rate of diffusion and phase separation. Polymer
and coagulant concentrations control the rate of diffusion. Diffusion rates for the
solvent and nonsolvent as well as the phase separation characteristics drive the
underlying transition.
As numerous factors contribute to the ultimate fiber properties, a wide
range of fibers can be formed. Particularly, shape, surface texture, luster and
physical properties can be altered. Even the wet process itself can be changed.
The dry-jet wet spinning procedure moves the spinneret prior to the coagulant,
allowing for a difference in dope and bath temperatures. This procedure also
reduces the fiber stress at the spinneret-coagulant interface of wet spinning.
Dry-jet wet spinning is suited for high production rates with a smaller number of
capillaries. The resulting structure resembles dry-spun fibers [7].
3.1.5 After treatment
Efforts to remove residual solvent and orient the fiber structure ensue
upon emergence of the dope stream from the coagulant bath. Such after
treatments consist of four general stages: washing, orientation, finishing and
relaxing.
Washing is another diffusion-driven stage, controlled by temperature and
concentration of wash liquid. Near-boiling water is typically used as the wash
bath. Generally, this stage occurs either before or in conjunction with stretching.
The fiber is purposefully left with residual solvent and a porous structure to
enable further processing in gel form.
Orientation changes the internal structure of the fiber and yields the final
fiber properties. This occurs at a fiber temperature elevated above the wet glass
transition temperature where the fiber is stretched 3 to 12 times between rolls
using water as the heat-delivery mechanism.
Finishing is used to facilitate further processing in the final relaxing stage
using lubricants and antistatic chemicals. Composition of the finish is dependent
upon end use. If applied before relaxation, finish chemicals inevitably diffuse into
the structure of the fiber via pores.
The relaxation stage also involves drying and collapsing. The sequence
of these steps depends on the fiber structure generated in the coagulant bath.
Invariably, the fiber collapses due to water removal and the pore structure is
closed. Crimp and relaxation are later applied to give cohesion and bulk to
yarns. Actual relaxation is the final change in fiber morphology through a hot,
wet treatment, which finally sets the mechanical properties of the fiber. Wet
crimp is followed by a one-step dry/collapse/relax treatment. Water is trapped
within the fiber pores as the fiber temperature is driven above the wet glass
transition. The fiber collapses and relaxes by means of water surface tension.
Specific finishing stages are highly cost driven. As the process is dependent
upon fiber structure in the spin bath, characteristics of the
polymer/solvent/nonsolvent system ultimately determine the fiber cost [7].
3.2 Dry Spinning
In contrast to wet spinning where nonsolvents diffuse into and solvents
diffuse out of the dope, formation of fibers by dry spinning occurs from solvent
evaporation. Evaporation is encouraged through a hot inert gas as the gel
passes out of the spinnerets. I.G. Farben AG first filed patents on the dry-
spinning use of DMF in 1942 as a solvent for polyacrylonitrile, which predated
patents filed by DuPont by only two months. World War II prevented Bayer from
producing it until 1954. DuPont and Bayer’s rights to the dry spinning procedure
created the impetus for other chemical companies to develop the wet spinning
procedure [4].
3.2.1 Process
A properly-mixed and de-aerated solution is pumped through the
spinneret. The most important stage in fiber spinning is the evaporation of the
solvent after the solution emerges from the spinneret. In dry spinning, the
spinneret is ring shaped to circulate the drying gas through the inner mount and
outside. The spinneret is made from stainless steel having generally 2800
apertures.
Once outside the spinneret, the solution quickly turns into gel as it
emerges in the spinning tube or cell. Here, the 6-10 m long, 250-450 mm wide
tube is heated using a jacket of diphyl (26.5% diphenyl, 73.5% diphenyloxide).
The drying gas, usually inert or saturated steam, is heated to 300-350°C flowing
with or against the direction of the gel. Gas must be circulated slowly, 1 – 2
m·sec-1, to avoid fibers from sticking together. Expected output is 8 – 15kg of
PAN solids per hour with up to 100,000 holes per spinneret and linear speeds of
100 m·min-1. Around 5 – 25% of the solvent is kept in the fiber to aid in further
processing. After sufficient solvent is evaporated, an oil finish is applied to the
filaments, drawn off by godet rollers and wound at 200 – 500 m·min-1 [4].
3.2.2 Solvents
For successful dry spinning, a number of factors must be considered.
First, the polymer must have sufficient stability at the solvent boiling point.
Secondly, the solvent should dissolve well, and not react with dissolved polymer
and have a low boiling point. Additionally, the heat of vaporization must be kept
low while having sufficient thermal resistance, low toxicity, low tendency to
induce static charge, low risk of explosion and easy to recover. Finally, cost
should not be prohibitive. Given these considerations, DMF was considered the
best solvent [4].
3.2.3 Polymer
The solvent content and temperature prevent orientation during the
spinning process. The overall degree of orientation during spinning increases
with the solution viscosity, spinning speed and spinning draft. It can also
decrease with time during material solidification forming microfibers. For product
uniformity, temperature must be well controlled in the spinning solution, spinning
head, drying gas and gas jacket [4].
3.2.4 Evaporation & Cross Sectional Shape
Solvent evaporates as the solution leaves the spinneret. Once in the hot
atmosphere of the spinning tube, the rate of primary evaporation must be
maintained slowly to prevent a sudden pressure drop. This can cause vapor
bubbles in the filament, which retards the fiber tensile properties.
Secondary evaporation occurs through diffusion. Material, concentration
and temperature-related diffusion coefficients should be controlled throughout
evaporation. Environmental conditions, take-up speed and length of time in
spinning tube determine the amount of solvent present in the gelled fiber.
Differential evaporation and diffusion rates create a solvent gradient with
the outer sheath solidifying faster. Further diffusion from the core reduces its
mass, causing the sheath to collapse inward. Equivalent diffusion and
evaporation rates create a circular cross section. A much faster evaporation rate
creates the bi-lobal, or dog-bone shape. Dwell time in the spinning tube also
affects the cross sectional shape. Longer time in the cell allows for more
diffusion to take place and more prevalent lobes [4].
3.2.5 After treatment
Final fiber properties are imparted in the last stages of processing.
Drawing, washing, finish and drying are the typical steps. Afterwards, fibers are
crimped and packed.
Drawing gives the as-spun fibers the orientation necessary for proper
mechanical properties including tenacity and breaking elongation. Fibers with
sufficient solvent content do not show a draw point, but must be stretched
adequately to impart full possible orientation. Fibers are stretched in boiling
water between one or two draw zones.
Washing begins before drawing where a tow can be exposed longer to the
washing bath. Washing is conducted under tension. Solvent diffuses out of the
fiber and into the water bath. Circulating the bath keeps solvent concentration
and temperature constant. Final residual content is less than 1% and generally
requires 20 washing zones and a total treatment time of 300 seconds. Finish
lubricates the fibers for further processing, imparts adhesion and prevents static
buildup.
Drying is necessary after washing to remove water. Final water content
should be 1 – 2%. PAN tows must be dried under tension to prevent shrinkage.
Contact heating via heated rollers is the preferred method of drying. Setting
begins at this stage, the degree of which depends on temperature and time and
is minimized to enable crimping. Crimping is generally conducted in a stuffer box
and provides sufficient adhesion between fibers. Tow is fed, heated, and the
fiber is forced to uniformly set [4].
3.3 Melt Spinning
3.3.1 Conventional Thermoplastics Processing
The three main stages for melt spinning polymers are preparation of the
melt, extrusion and winding. A molten polymer is forced through a spinneret
orifice at a given temperature, pressure and rate. The flow is collected at a
different velocity at the site of ‘take-up.’ The distance between the spinneret and
take-up is variable. Once the polymer reaches the take-up area, the process of
initial fiber formation through solidification and cooling is finished.
From high production rates and absence of required equipment, of all
types of fiber spinning methods, melt spinning is the most economical. The only
caveat is having a thermally-stable and coherent polymer in molten stream form.
Unlike wet- and dry-spinning, there is generally no mass transfer between
polymer and surroundings. Steady state is then defined as the product of
density, cross-section area and velocity of the spinning line at a given distance
from the spinneret. Numerous variables are defined that influence the properties
of the fiber. Ziabicki outlines constituent parameters of three categories: 1)
primary, 2) secondary and 3) ‘resulting’ [9].
Primary variables are concerned with predetermined technical settings
that establish the foundation for the extrusion. The most important primary
variable is the material thumbprint such as chemical composition, molecular
structure and physical behavior. Other associated variables are the extrusion
temperature, dimensions and number of spinneret orifices, mass outflow, length
of spinning path, take-up velocity and cooling conditions.
The secondary variables relate to the equation of continuity between
density, area and velocity. In particular, extrusion velocity, average diameter and
titre of the as-spun filament and the spin-draw ratio, or ratio of take-up velocity
and extrusion velocity, are the defined variables.
The resulting variables follow from the kinematics and dynamics of the
spinning process. These characteristics include take-up tension, take-up stress,
ultimate filament temperature, and any other texture or physical properties of the
as-spun fibers [9].
3.3.2 Imparted melt processability
For PAN, melt processability can be imparted if the melting point is
brought sufficiently below the degradation point. One of the most direct ways is
inclusion of 5 – 20% of low molecular weight polyacrylonitrile or incompatible
lubricating component such as a polyolefin or polyamide. However, these
materials can adversely affect the mechanical properties and chemical
resistances of the resulting fiber.
Copolymerization to reduce the melting point has been investigated since
the early 1950s. However, the distribution of comonomer in the copolymer
structure allowed in traditional free radical polymerization reactions prevented
success. One successful attempt utilized acrylic esters or methacrylic esters in
emulsion polymerization, where after fiber conversion, 11% of the polymer was
extracted with acetone. The melt was spun at 1500 m·min-1 at 200 ºC with a 1.8
denier fiber and tenacity of 4.5 gf·den-1.
3.3.3 PAN Hydrates
Water decouples the dipole interaction between the acrylonitrile
sidegroups and has been employed in an attempt to produce melt-spun fibers
from a high pressure (30 to 70 bar) system. PAN exists in four primary phases,
depending on temperature and contact with water: solid, hydrate, dual and
suspension. At temperatures above 150ºC and water contents between 5 and
25%, the hydrate form is a metastable single phase where water evaporates out
of the hydrate stream to form fibers. The throughput rate is thus a function of the
rate of evaporation.
Mechanically, the fibers have a tenacity of about 4.5 gf·den-1 and a
breaking elongation of 40%. This fiber also has an irregular cross-section.
Quality as well as economic issues, such as pressure, throughput and energy
consumption, are obstacles that prevented implementation of this technology [4].
3.3.4 Summary of Prior Art in ‘Melt Processable’ PANs
Over recent decades, foreign and U.S. patent offices granted hundreds of
patents relating to melt processability of high acrylonitrile-content polyacrylonitrile
and related variants. Nearly all, except for those relating to Amlon®, focus on
imparting melt processability through copolymerization with post-conversion
solvent extraction, reduction of melt viscosity by inclusion of low-molecular
weight acrylonitrile polymers, copolymerization to reduce melting point, PAN
hydrates, and inclusion of incompatible lubricants and other plasticizers.
Markets and Potential 30
4 Markets and Potential
A thermoplastic version of high polyacrylonitrile has been sought for many
decades. However, the anomalous paracrystalline morphology and lack of ability
to control the structure of the copolymer prevented an innately thermoplastic form
from being available. Now that a process for structuring the polymers has
emerged, the larger potential for the material can be explored.
4.1 Trends in the Worldwide Synthetic Fiber Production
Worldwide consumption of synthetic fibers shows clear trends for the past
10-15 years, Figure 2. Polyester, or poly(ethylene terephthalate), continues to be
the largest fiber in production and the fastest growing. Filament rather than
staple is the most popular form. Polyolefins including poly(ethylene) and
poly(propylene) show steady growth since 1994. Aramids, nylon (PA) filament,
acrylic, and cotton fibers show nearly constant consumption.
4.2 Trends in the Acrylic Fiber Market
In the decades following the introduction of acrylic fibers by DuPont in the
1950s, the U.S. marketplace grew rapidly. Only years after the release of
Orlon®, six other companies released their own acrylic fiber: Union Carbide’s
Dynel®, Monsanto’s Acrilan®, American Cyanamid’s Creslan®, Dow Chemical’s
Zefran®, Tennessee Eastman’s Verel® and Goodrich’s Darvan® [10]. The primary
uses of acrylic fibers were for wool replacements in carpet, bulk fabrics and
blankets.
25
Production (millions of metric tons)

20
15
10
1994 1996 1998 2000 2002

Acrylics Year Nylons
Polyester Polypropylene
25
20
15
10
1985 1990 1995 2000 2005

Acrylic & Modacrylic Nylon & Aramid
Year
Polyester Polyolefin
Figure 2. Synthetic Fibers Market: Acrylics, Polyester,

Nylons, Aramids, and Polyolefins
a) Worldwide Consumption [11]

b) Worldwide Consumption, [12-19], a excluding U.S. Aramids
4.2.1 Markets in the United States
After the initial peak in usage, the market subsequently declined in the
early 1970s as nylon outperformed acrylic in terms of elastic recovery. Given the
type of wear in carpet applications, recovery of the fiber to its original shape is
highly desirable. The first large overcapacity for acrylic fiber production ensued.
Consequently, producers shifted their efforts to the apparel fibers market, which
itself peaked in the 1980s. However, the popularity of cotton in sweaters and
socks caused the second decline in the acrylic fiber market. Due to a gross
world overcapacity, DuPont began closing foreign manufacturing sites in 1978,
which continued until 1990 when it exited the acrylic business altogether.
Producers became increasingly dependent upon foreign exports to Western
European and Japanese markets, Figure 3. However, consumption in foreign
markets gradually declined, Figure 4, and domestic operating capacity followed
suit. Gross worldwide overcapacity eroded profit margins and producers of
commodity acrylic fibers closed operations, spun-off companies or sold assets.
During the late 1990s, the remaining descendants of the first producers of acrylic
fibers – American Cyanamid and Monsanto – divested their fiber businesses.
Sterling Chemicals [20], Inc. purchased Cytec’s assets in 1997, which itself was
a 1993 spin-off of American Cyanamid [21]. Solutia, Inc., was Monsanto’s 1997
chemical spin-off [22] and until 2005, they were the only two major commodity
acrylic fiber U.S. producers [23]. On February 2, 2005, Solutia closed its
remaining production site, exiting the acrylic fiber business [24].
Amount (thousands of metric tons)

400
300
200
100
1975 1980 1985 1990 1995 2000 2005

Year
Capacity Production Domestic Shipments

Imports Exports Consumption
Figure 3. Capacity, Production, Domestic Shipments, Imports, Exports and

Consumption in United States Acrylic Fiber Market.
[23]
600

500
400
300
200
100
1980 1985 1990 1995 2000 2005

Year
1500
1250
1000
750
500
250
1980 1985 1990 1995 2000 2005

Year
Capacity Production Consumption
Figure 4. Capacity, Production and Consumption in the Acrylic Fiber

Markets by Major Geographical Regions
a) Asia [23].
b) China [23].
600

500
400
300
200
100
1975 1980 1985 1990 1995 2000 2005

Year
500
Amount (thousdands of metric tons)
400
300
200
100
1970 1975 1980 1985 1990 1995 2000 2005

Year

Markets by Major Geographical Regions. (continued)
c) United States [23].

d) Japan [23].
1250

1000
750
500
250
1970 1975 1980 1985 1990 1995 2000 2005

Year
Markets by Major Geographical Regions (continued)
e) Western Europe [23].
250
200
150
100
50
1975 1980 1985 1990 1995 2000 2005

Year
Figure 5. Acrylic Fiber Consumption by Apparel, Home

Furnishings and Industrial Market Segments.
a) United States [23].
100
Amount (thousdands of metric tons)

75
50
25
1990 1995 2000 2005

Year
500
400
300
200
100
1985 1990 1995 2000 2005

Year
Apparel Home Furnishings Industrial & Other
Figure 5. Acrylic Fiber Consumption by Apparel, Home

Furnishings and Industrial Market Segments. (continued)
b) Japan [23].
c) Western Europe [23].
25

20
15
10
1994 1996 1998 2000 2002

Acrylics Year Nylons
Polyester Polypropylene
25
20
15
10
1985 1990 1995 2000 2005

Acrylic & Modacrylic Nylon & Aramid
Year
Polyester Polyolefin
Figure 6. Synthetic Fibers Market: Acrylics, Polyester,

Nylons, Aramids, and Polyolefins
a) Worldwide Consumption [11]

b) Worldwide Consumption, [12-19], a excluding U.S. Aramids
4.2.2 Markets in Europe and Asia
Consumption of acrylic fibers in the traditional markets – the United
States, Western Europe and Japan – continues to contract. Strong exports
characterize these markets, where traded fibers are more application specific.
The use of acrylic fibers in Western Europe tends to be bulk fabrics, Figure 5.
Japanese use is mainly carbon fibers. The balance of these exports finds buyers
in China, where consumption is rapidly accelerating. In 2000, China became not
only the largest consumer of acrylic fibers worldwide, but consumed more acrylic
fibers than all other combined acrylic worldwide markets with 840,000 million
metric tons. While their production is increases, the gap between consumption
and production grows. While the demand to import fibers into China is
increasing, the pervading worldwide overcapacity prevents some from remaining
in operation. Indonesia shows the second largest consumption of acrylic fibers at
120,000 metric tons in 2004 [23]. India is the third largest Asian market, whose
annual consumption of acrylic fibers was only 102,000 metric tons, or
approximately 8.5% of China [25].
4.2.3 Market Prospects
In a market with this history, a new acrylic fiber must have substantial
benefits. Cost savings will be an important aspect, as solution processing
contains inherently more costly procedures than melt processability. Other
factors for success in fiber markets are improved mechanical properties. In
product markets where acrylics are widely used, such as outdoor fabrics,
manufacturing textiles from filaments rather than staple yarns should decrease
the overall production costs. If the fiber performs better, specifically in tenacity,
washability, crease-ability, and elastic recovery, low raw materials cost could
make it a less-expensive alternative to polyesters and/or nylons. Furthermore, in
addition to fibers, a melt-processable material will offer many new alternatives in
the wider thermoplastic polymer markets of films. Polyacrylonitrile would then
offer its unique properties – namely UV and chemical resistances – and improved
mechanical performance in a commodity, thermoplastic form.
4.3 Cost Analyses
The benefits of melt processing, aside from mechanical enhancements,
are cost driven. The least expensive manufacturing route is synthesis of the
polymer followed by direct conversion to fibers. Cost predictions of melt
processable high acrylonitrile are based on raw materials and estimated
conversion costs for poly(ethylene terephthalate), polypropylene, and polyamides
or nylons. The results are presented in Table 1.
4.3.1 Poly(ethylene terephthalate)
Poly(ethylene terephthalate) is synthesized from ethylene glycol (EG) and
dimethyl terephthalate (DMT) or purified terephthalic acid (PTA). Polymerization
with PTA is now the dominate method because of shorter reaction times and
reduced amounts of required catalyst. Polyester fibers have the largest
worldwide demand with approximately 20.9 million metric tons in 2002.
Approximately 0.39 pounds of EG and 0.90 pounds of PTA are required per
pound of synthesized PET [26, 27]. Raw material, resin, filament and staple
costs are shown in Figure 7 a). From 2000 – 2003, the average conversion cost,
or difference between filament and raw material costs, was 27 cents·pound-1.
4.3.2 Poly(propylene)
Polypropylene, a polyolefin, is synthesized directly from propylene with
assistance of metallocene catalysts that enable molecular weights and bulk
properties to be engineered. It is one of the easiest polymers to handle and
fastest growing segments of the synthetic fiber industry with 2002 production just
under 6 million metric tons [28, 29]. Approximately 1.01 pounds of polymer-
grade propylene are required for each pound of polypropylene. Raw material,
resin and various fiber and yarn costs are shown in Figure 7, b). Since 2000 the
average conversion cost, or difference between raw materials and polymer resin
was 15 cents·pound-1. A lower conversion cost, when compared with PET, is
due to the difference in final product (resin versus filament) and the higher
operating temperature required to process molten PET.
4.3.3 Poly(amides)
Polyamides, or nylons, are a general term for related chemical structures.
They are named for the number of carbon atoms between the two amide bonds.
Nylon 6 and Nylon 66 are the predominate forms with somewhat different
properties, accounting for nearly 98% of the worldwide nylon production. Nylon 6
is synthesized directly from caprolactam requiring 1.01 pounds per pound of
Nylon 6. Nylon 66 is synthesized from adipic acid and hexamethylenediamine
requiring 0.73 and 0.57 pounds per pound of polymer, respectively [30]. Nylon
fibers have some of the highest tenacities of commodity fiber-forming polymers,
ranging from 4.5 – 5.5 gf·den-1. In 2000, over 4 million metric tons of nylon fiber
was produced. Raw material, resin, and fiber costs are shown in Figure 7, c).
4.3.4 Solution processable high acrylonitrile copolymers
While the cost of raw polyacrylonitrile materials – chemical grade
propylene and ammonia – is the lowest raw material cost among the major
thermoplastic fiber-forming polymers. Trends in raw materials, intermediate and
fiber costs are shown in Figure 7, d). In 2002 the cost was approximately 19
cents·pound-1 [31], versus 20 for the polymer-grade propylene used in
polypropylene. However, 1.2 pounds of chemical grade propylene are required
for one pound of acrylonitrile, bringing the raw material cost to 22 cents·pound-1
versus a similar 20 cents·pound-1 for polypropylene, whose difference changes
where the cost of chemical and polymer grade propylene vary somewhat
independently.
Solution-spun fibers tend are relatively expensive, and acrylic fibers cost
approximately 85 cents·pound-1 in 2002 [23]. Low throughput ( 200-500 m·min-1
[4]) and solvent recovery are the primary factors that drive the higher prices.
Since 2000, the cost of conversion from raw materials to fiber was 58
cents·pound-1.
4.3.5 Melt processable high acrylonitrile copolymers
In acrylic copolymers, inclusion of comonomers will increase the cost of
the resin. In 2003, the cost of vinyl acetate was 48 cents·pound-1 [32] and methyl
methacrylate 65 cents·pound-1 [33]. In 1994, methyl acrylate was 12
cents·pound-1 more expensive than methyl methacrylate [34], putting the current
price probably between 70 to 80 cents·pound-1. While methyl acrylate and vinyl
acetate are similar chemicals, despite its higher cost, methyl acrylate was the
original comonomer used in Orlon® [10], is still used in Dralon® and is the
comonomer used for the Amlon® D copolymer in this study. Based on the most
recent prices, the raw material cost for an 85% acrylonitrile acrylic copolymer
would lie between 29 and 31 cents·pound-1. In 2002, the raw material costs of
poly(ethylene terephthalate) was 36, nylon 6 72 cents·pound-1, and nylon 66 117
cents·pound-1. Thus, the raw materials for acrylonitrile are the second least
expensive of commodity synthetic fibers.
While a more detailed costing of acrylic fibers by comonomer and
acrylonitrile content was not given, this conversion cost should be considered an
estimate for solution processing acrylics. The conversion cost for the other
synthetic fibers depends on the continuity of production. Since 2000, the mean
conversion cost or difference in fiber and raw material costs for solution-
processed acrylic is 58 cents·pound-1. Likewise, the mean conversion cost of
raw materials to resin was 40 cents·pound-1 for unsaturated poly (ethylene
terephthalate), 15 cents·pound-1 for polypropylene, nylon 6 53 cents·pound-1,
nylon 66 21 cents·pound-1, and polypropylene 15 cents·pound-1. Given these
costs of converting the raw materials to a resin and the raw material cost for
acrylonitrile, the expected cost of melt processable polyacrylonitrile resin might
be between 45 and 65 cents·pound-1, depending on the efficiency of
polymerization and type of comonomer produced.
Table 1. Raw Materials and Conversion Costs for Major Thermoplastic Polymers
Raw Cost Conversion Costs (¢·lb-1)
Resin Materials
(¢·lb-1) Resin Fiber
Ethylene glycol and
Stp: 19
PET (dimethyl terephthalate or 36 40
Fil: 27
purified terephthalic acid)
PP Polymer grade propylene 22 15 n/a
6: Caprolactam
6: 72 6: 53
PAs 6,6: adipic acid and Fil: 21
6,6: 117 6,6: 21
hexamethylenediamine
Chemical grade propylene
coPNAs ±30 n/a Stp: 58
and ammonia
Chemical grade propylene Stp: 20 – 30
Amlon® ±30 45 - 65
and ammonia Fil: 30 – 45
For carpets, where polypropylene and nylons dominate, the cost of
conversion is approximately 78 and 74 cents·pound-1. Thus melt processable
polyacrylonitrile carpet yarns are expected to cost between 110 and 125
cents·pound-1, putting it between the low end and high end markets where
properties and cost may expropriate market share the competitors. Since 2000
for fibers, the mean difference in filament and raw materials cost for
poly(ethylene terephthalate) was 27 and staple 19 cents·pound-1. The difference
in an undesignated type of nylon in staple form and nylon 6 raw material cost
was 21 cents·pound-1. Given these costs and based on the estimated raw
material cost for acrylonitrile copolymers, the projected cost for melt processable
polyacrylonitrile filaments is 60 to 75 cents·pound-1 and staple 50 to 65
cents·pound-1. The staple cost corresponds with the extra cost of solution
processing – approximately 20 – 30 cents·pound-1.
120
100
Cost (cents per pound)

80
60
40
20
1980 1985 1990 1995 2000 2005

Year
Raw Materials Unsaturated Resin
Filament (150 denier) Staple
250
200
150
100
50
1980 1985 1990 1995 2000 2005

Year
Raw Materials Homopolymer Resin
Carpet Face Yarn (2750 denier) Upolstry (fine denier)
Sanitary Applications (1.5-2.2 den) Needlepunched Geotextiles (5-8 den)
Figure 7. Raw Material, Intermediary and Fiber Costs for Poly(ethylene

terephthalate), Poly(propylene), Poly(amides) and Polyacrylonitriles.
a) Poly(ethylene terephthalate) [26, 27, 35, 36].

b) Poly(propylene) [28, 29, 37].
300
250

200
150
100
50
1980 1985 1990 1995 2000 2005

Year
Nylon 6 Raw Materials Nylon 66 Raw Materials Nylon 6 Resin
Nylon 66 Resin Carpet Yarn (1200 den) Textile Yarn (40 den)
125
100
Cost (cent per pound)
75
50
25
1980 1985 1990 1995 2000 2005

Year
Raw Material Acrylonitrile List
Acrylonitrile Contract Acrylic Fiber (3 denier)
Figure 7. Raw Material, Intermediary and Fiber Costs. (continued)
c) Poly(amide), Nylons [30, 38-41].

d) Poly(acrylonitrile) [23, 29, 31].
4.4 Potential Applications for Thermoplastic PAN
Historically, high cost, low throughput and difficult processing prevented
polyacrylonitrile from reaching its full potential as a commodity polymer. Few
unmodified vinyl polymers offer such characteristic properties, especially those of
chemical and UV resistances. Fluorinated and chlorinated chains are notable
alternatives, each having their specific uses, which are dependent upon their
unique chemistries.
4.4.1 Comparative properties between synthetic fibers
Poly(ethylene terephthalate) filament and staple fibers are used as the
benchmark, because they dominate the synthetic market and its tenacity and
density are considered relatively high, Table 2 and Figure 2. It has good UV
resistance, abrasion resistance and strength, and exceptional wash-wear
performance, wrinkle resistance and resistance to burning [42]. Nylons are
specialty fibers finding use in industrial applications and products where elastic
recovery is important. They are known for exceptional abrasion resistance,
strength and elastic recovery, but poor resistance to UV radiation. Polypropylene
is an inexpensive, easy-to-handle fiber with standard mechanical properties.
They are difficult to dye and are unable to hold creases. Acrylics are not
traditionally known for high strength. However, they do exhibit excellent hand,
bulk, wick-ability, UV and chemical resistances.
4.4.2 Deniers, profiles and multicomponent fibers
Properties of fibers and fabrics depend not only on the chemistry of the
fiber, but often times more importantly on their physical structures. A large
diameter, for instance yields a higher bending rigidity, which is helpful in some
mechanical applications. However, fine denier fibers are useful for good draping
and soft hand. Finally, optical properties are dependent not only on the diameter,
but on the shape of the fiber. The latter affects the way light is reflected or
refracted, which creates optical illusions.
Table 2. Comparative Properties of Synthetic Fibers

Tenacity Elongation Specific Moisture
Fiber
( gf·den-1 ) (%) Gravity Regain (%)
Poly(amide) [30] 4.5 – 5.6 25-33 1.14 4.0 – 4.5
Poly(ethylene terephthalate) [35] 4.6 – 5.0, 8.9 20-55, 12 1.38 0.4
Poly(propylene) [43] 3.0 – 4.0 80 – 100 0.91 0.0
Poly(acrylonitrile) [23] 2.5 – 4.0 20 – 55 1.16 – 1.18 1.0 – 2.5
Traditionally, acrylic fibers are either bi-lobal or round. With a
thermoplastic form, diameters can be shaped as tri-lobal, or any other kind of
profile. Fibers with desired luster can thus be obtained, specifically for carpets.
Already, some Amlon® fibers have been observed to have high lustrous
properties. Since the density of acrylic copolymers, which is dependent upon the
type and concentration of comonomers, is similar to nylon [44], a standard in
fashion fabrics, lightweight lustrous fabrics from Amlon® can also be constructed.
As denier not only affects the mechanical and optimal properties,
decreasing diameter also provides more surface area. Nano- and microdenier
fibers ( < 1 denier per fiber [45] ) are typically made from bi- and multicomponent
systems. The fibers and fabrics are often used to achieve suede hand, filtration
and in absorptive applications [46]. Amlon® would potentially enable a range of
new technical fabrics from material containing a high content of acrylonitrile with
the characteristic resistant properties.
4.4.3 Reinforcing fiber
Acrylic fiber tow finds application as reinforcement for cement and
concrete products. The polymer should be 100% acrylonitrile to hinder
decreases in tenacity and modulus from warm-moist effects [6]. Meltability of a
fiber may not be advantageous in applications that demand consistent
mechanical behavior in hot and wet environments. Furthermore, high molecular
weights, whose range is between 100,000 and 500,000, are typically used. This
can significantly increase solution viscosity and would likewise increase melt
viscosity. A melt-processable PAN might not be suited in this application.
4.4.4 Carbon fibers
Similar to reinforcing fibers, very high molecular weights of
polyacrylonitrile (and copolymers with low concentrations of comonomers) are
necessary to ensure suitable tenacity and modulus of carbon fibers [6, 47], which
range from 2550 to 4000 MPa and 230 to 600 GPa, respectively. Furthermore,
low content of comonomer (2 – 5%) are in carbon fiber precursors. As such,
viscosity and processability in a thermoplastic form may be problematic.
Furthermore, the conversion of precursor fibers to carbon fibers involves a
thermomechanical stabilization treatment in order for successful pyrolysis to
carbon. During this stage, the fiber is placed under low tension and slowly
heated to 260 – 290ºC while the polymer chains cyclize to form an imine
structure and then oxidize to form a pyridone structure. In other words, the
sidegroups collapse and cross link to form an intermediate conjugated structure.
The nitrogen in the acrylonitrile sidegroup loses its triple bond to form a double
bond with its partner carbon and forms a single bond with the carbon in the
sidegroup of the neighbor. The cyclized structure is oxidized to maintain its
stability during pyrolysis.
This process of thermomechanical stabilization has emerged specifically
for the traditional solution-processed acrylic fiber. Therefore, it is possible that a
similar mechanism of stabilization may be unsuccessful in converting a melt
processable fiber at temperatures above its melting point. For polyacrylonitrile,
alternative forms of oxidation stabilization involve UV radiation, gamma
irradiation, and chemical treatment, the former was investigated by Paiva for
Amlon® [48].
Pitch is an alternative carbon precursor material made from petroleum and
coal byproducts and finds application in high modulus carbon fibers (100-1000
GPa). As it is melt processed, albeit at a higher temperature, similar stabilization
difficulties are present. Pitch fibers are successfully thermomechanically
oxidized materials, whereby the mechanical properties are best when oxidation is
optimized. For Amlon®, a new procedure for stabilization and oxidation must be
developed. Guidelines for an appropriate technique may be found in existing
technologies.
As the Amlon® technology includes olefinically unsaturated monomers,
comonomers like itaconic acid that are more appropriate for carbonization may
be investigated. The amount of comonomer and the associated bulk properties
require engineering for specific applications. In summary, the use of Amlon® for
carbon fiber technologies will likely require significant and long-term
development.
4.4.5 Composite and carbon carbon composite components
Amlon® will likely find application in the larger field of composites and
carbon carbon composites. Various thermoplastic, thermoset and epoxy
matrices are employed in a wide range of composite applications from pultruded
to laminated products [49]. The existence of a thermoplastic polyacrylonitrile
would provide a low cost carrier where UV and chemical resistance is
advantageous. In particular, marine, aerospace, automobile, and consumer
product industries are probable candidates.
While Amlon® may require a more specific method of conversion to carbon
fiber, it may also serve as a carbonaceous matrix in carbon carbon composites
(CCC). CCCs are constructed using carbon fibers suspended in a carbon
precursor matrix. Aside from superior mechanical properties in a lightweight
material, CCCs are also known for their thermal and electrical conductivities. As
such, they are employed in various aerospace and high tech applications.
CCCs are fabricated using two main techniques: gas phase infiltration
(GPI) and liquid phase infiltration (LPI) [50]. In GPI, the composite is heated in a
furnace up to 1100 ºC where hydrocarbon gas is circulated. A “crust” is gradually
deposited in the substrate surface. In LPI, matrices are typically either pitch or a
thermoset resin like phenol formaldehyde. The composite is oxidized and
converted to carbon and densified by filling voids that are created during
degassing of carbonization byproducts within the matrix. Densification usually
involves two or three stages to ensure a consistent structure. Low viscosity
phenol is used in monolithic composites, whereas pitch is impregnated in thin-
section carbonaceous preforms. The material choice depends on the application
and cost. Amlon®, similar to pitch, may offer a matrix alternative for partially or
fully carbonized composite materials where the achievable conductive,
mechanical and resistant properties may be optimized.
4.4.6 Limitations from the hot-wet conundrum
One of the main reason that traditional acrylic failed to maintain a
dominant presence in the apparel and carpet markets is that the fibers are
unable to retain their moduli in hot-wet conditions [5]. This leads to a loss of bulk
and shape after repeated washing and drying. Under humid conditions, fibers
lose their resilience and wrinkles develop that are difficult to remove. Over time,
this causes the fabrics to lose their original shape. This property is attributed to
changes in glass and melting temperatures in the presence of water. Numerous
methods of improving this property have been attempted with limited success.
4.4.7 Outdoor fabrics
Due to the exceptional UV resistance in high acrylic fibers, their fabrics
find use in many outdoor applications. Primarily, products include awnings,
convertible automobile covers and marine textiles woven mainly from ring-spun
yarns. A melt-processable acrylic would enable these products to be made less
expensively through lower material costs, use of filaments rather than staple
fibers, or through nonwovens fabrics.
4.4.8 Nonwovens
To date, almost all acrylic fiber nonwovens are constructed from wet-lay,
air-lay or carding processes. However, the amount of melt spun nonwoven
production (at least in the U.S. and Canada) has steadily increased [51]. A
thermoplastic polyacrylonitrile would potentially open the melt spun industry to
acrylic for fabrics, filtration [46] and high tech products including carbonized
fabrics. The specific technologies used are dependent upon the product, which
relates to the fiber denier [52]. Cold drawing, a phenomenon required for melt
blown technology, has been observed in Amlon®.
4.4.9 Membranes, Films and Conductivities
Membranes are constructed in many forms for specific properties and
applications [53]. One of the methods that pertains to fibers is hollow fiber
membranes (HFM). HFMs are advantageous because they allow a high
modulus composite with high surface area. The diameter of the fiber ranges
from 50 to 3000 µm and is typically used in pressurized gas filtration,
hemodialysis or separation of particulate matter. While these fibers are typically
solution-spun, Amlon® may provide an easier method of fabrication.
The application of selectively permeable membranes in filtration for media
and for protection against biological and chemical warfare agents is fast
increasing. For many applications, chemical resistance is a desired property.
The cost and thermomechanical properties of the polymer often restrict the
application. A commodity thermoplastic, polyacrylonitrile may offer a higher
performing, material in terms of chemical and UV resistances, for less cost.
The enhancement of properties through grafting, doping and inclusion of
specific comonomers for electronic conductivity has been demonstrated for
acrylic fibers [5]. In several Japanese patents, electrically conducting fibers have
been made using metal dopants. Furthermore, the inclusion of sulfur
comonomers into acrylonitrile copolymers for improved dye-ability is well known
[34]. Fluorosulfonated semi-permeable membranes known as Nafion® have
dominated the ion exchange membrane market for polymer electrolyte fuel cells
[54]. The material is able to resist the corrosive environment, but its performance
is limited because of the inherent hydrophobicity of the polymer, which reduces
its ability of allowing hydrogen ions to cross the membrane. As polyacrylnotrile is
chemically resistant, while being hydrophilic, it may offer a better performing
alternative.
Regardless of whether the membrane, essentially a thin film, is used to
restrict the passage of chemicals, the gamut of less sophisticated film and
bottling applications are also possible. Today, materials with less than 85%
acrylonitrile are used in a well known barrier film under the trade name Barex®.
With the resistances unique to high acrylonitrile copolymers, low material cost
and mechanical property enhancements inherent to melt-processability, better
performing filaments, new thermoplastic applications and high tech markets are
likely.
Polymer Microstructural Analyses 57
5 Polymer Microstructure
Polyacrylonitrile (PAN) is a unique vinyl polymer because of its chemical
resistance and semi-crystalline morphology. One of its most notable properties
is its relatively high ‘melting’ point of ~320º C and low thermal degradation range
from 250 - 310º C [55]. For most thermoplastic polymers the relationship
between crystalline morphology and melting point is well understood in terms of
discrete crystalline and amorphous domains and as an equilibrium first-order
thermodynamic phase transition [56]. However, PAN does not exhibit the
classical two-phase morphology and has been described as “amorphous with a
high degree of lateral bonding” [57], or as a “two-dimensional liquid crystalline-
like structure with many defects” [58]. As a result, and despite conflicting
conclusions about its tacticity as radically-polymerized [59-61], the degree of
crystallinity for the homopolymer does not appear to be a function of
stereoregularity [62]. Similar behavior is also observed in poly (vinyl alcohol) and
poly (norbornene) [63].
Unlike other vinyl polymers, where stereoregularity is required to
crystallize [64], this mesomorphic crystalline polymer exhibits lamellar single-
crystal-like platelets [65] and a variety of lattice structure morphologies that are
independent of stereoregularity [55]. It does not exhibit regular ‘melting’
thermograms, except when using differential scanning calorimetry at a high ramp
heating rate of 160 ºC·min-1, where it shows what appears to be an endotherm
prior to exothermic degradation reactions [5].
The first order thermodynamic melting transformation, is defined by
∆H m
Tm = ,
∆S m
where Tm, ∆Hm and ∆Sm are the temperature, enthalpy and entropy of melting,
respectively. In terms of equilibrium melting, the interchain interactions between
polar nitrile substituents, which must be incorporated in the PAN crystals, are
expected to contribute primarily to the enthalpy of melting. The change in
entropy upon melting, on the other hand, is associated mainly with disordering
the intrachain PAN conformations [66]. Measurements of melting point
depression in dilute solution show that the heat of fusion of PAN is less than that
of poly (chlorotrifluroethylene) and much less than that of polyethylene [67],
implying that substantial interchain interactions between nitrile substituents
persist in the PAN melt. Because of its high Tm and relatively small ∆Hm, the
change in entropy upon melting PAN must be very small [68], which is consistent
with substantial conformational freedom or diversity for the PAN chains even
when incorporated in crystals.
In general, to alter the crystal morphology and melting temperatures of
homopolymers, comonomers are used to reduce the copolymer melting
temperature. Theoretical works by Flory and by Eby suggest microstructural
control of copolymer melting temperatures. Flory asserts that comonomer
interruption and shortening of the length of the crystalline monomer sequences,
reduces the number and average size of crystallites [69]. Because chain
segments on the crystallite surfaces have larger free energy, smaller crystals
with a larger surface to volume ratio have a reduced melting point [58].
Specifically, the crystallizable monomer sequence length decreases linearly with
the addition of the comonomer:
1 1 R
− o= XB,
Tm Tm ∆H u
where Tm and Tmº are the melting points of the copolymer and homopolymer,
respectively, R is the universal gas constant, ∆Hu is the heat of fusion per mole of
crystalline repeat unit, and XB is the mole fraction of the minor non-crystallizing
comonomer. Furthermore, for non-random copolymers, Flory proposes that the
melting point depression depends on the sequence propagation probability and
not the overall comonomer composition (XB) [70]. Eby, on the other hand,
proposes that the comonomer may be partially incorporated into the crystal
lattice as defects and extends Flory’s theory by adding a parameter that accounts
for the degree of lattice disruption [71].
For PAN copolymers there exists evidence in support of both theories. In
support of the Flory theory, Slade, et al. experimentally verified the relationship
between the depression of melting temperature and comonomer concentration
for vinyl acetate/AN copolymers [72]. Kulshreshtha, et al. showed that
crystallinity and crystal thickness decrease with larger concentrations of methyl
acrylate comonomer [73], until the structure is highly disordered [74]. Frushor
demonstrated evidence in support of the Eby theory with a melting point
depression constant, which indicates the degree to which comonomers disrupt
the crystalline lattice, based on the molar volume of their sidegroups [74].
To date, the only reported way to affect the PAN melt temperature is
through controlling the parameters of free radical polymerization, including
monomer concentrations and reactivities. The enchainment of comonomers and
their sidegroups in the resulting copolymers are considered to be sequenced in a
somewhat blocky manner, and are not completely randomly inserted [75]. At a
comonomer concentration over 15%, methyl acrylate or vinyl acetate create a
modified acrylic, or modacrylic, which at sufficiently high incorporation produces
an amorphous glassy material. To the extent that the thermal properties are
dependent upon the length of the acrylonitrile sequences, a melt processable
high PAN (high AN content) is possible if the lengths of the AN sequence were
controllable, such that they are long enough to impart crystallinity, while keeping
the melting point below the degradation range. This would support the proposal
by Flory that in this non-random copolymer, the sequence propagation
probability, which determines the average AN length, controls the melt behavior.
The crystalline domains could, however, still include the comonomer as indicated
by Eby and Frushour.
British Petroleum (BP) scientists Smierciak [76], et al. developed a novel
‘starved’ or ‘scavanged’ emulsion copolymerization reaction based on work by
Dimitratos [77]. Under extremely low feed rates, the polymerization rate
approaches a pseudo-steady value based on the availability of the monomer and
its addition rate, and the composition of the copolymer is similar to the
comonomer feed concentrations. Using this technology, in the 1990s BP
developed and patented a family of thermoplastic high polyacrylonitrile resins
called Amlon®. BP claims that for a given copolymer composition, the sequence
length of the AN sidegroups can be reduced sufficiently to enable melting.
When comparing the resultant copolymers from ‘scavenged’ and
traditional ‘flooded’ copolymerization reactions, the resulting structure of the
former would shift towards more regularly-alternating structures, because the
number of junctions between methyl acrylate and acrylonitrile junctions increases
and the distance between junctions is reduced. PAN crystallinity is generally
considered a result of the interactions and packing of acrylonitrile side groups, so
this less blocky structure would disrupt the pseudo-crystalline order more
frequently. Since the melting temperature of PAN copolymers has been shown
to be a function of the AN sequence length and if controlling the length is now
possible, a PAN copolymer could be made such that an optimum balance
between sequence length and melt temperature is achieved.
5.1 Experimental
5.1.1 Materials
The Institute of Textile Technology, at North Carolina State University,
Raleigh, NC now holds worldwide patent rights to Amlon® technologies. Amlon®
D resin is an 85% acrylonitrile : 15% methyl acrylate copolymer with a molecular
weight between 50k and 60k [78].
Dralon® type 251 bright 1.3 dtex of 93% acrylonitrile : 7% methyl acrylate
was supplied by Dralon GmbH, Dormagen, Germany. Exxon Mobil
polypropylene type 16050 was used to compare viscosities.
5.1.2 Solution 13C Nuclear Magnetic Resonance (NMR)
An Oxford Instruments 300 MHz for protons NMR spectrometer using 1H-
13
decoupling was used to collect C spectra. Type 507-HP round bottom NMR
sample tubes from Norell, Inc. were used. Approximately 50 mg of undried
Amlon® D and Dralon® fiber were dissolved in 0.6mL of deuterated d6-dimethyl-
sulfoxide. Spectra were recorded at 120º C and 20,000 scans were collected
[79].
The number average sequence length of acrylonitrile monomer units in
Amlon® D was determined from the experimentally observed comonomer triad
concentrations [80], using the following relation:
N101 + N001 + N000

n0 = [81],
1
N101 + N001
2
where n0 is the number average sequence length of acrylonitrile (A) units, and
N101 , N001, and N000 the concentrations of MAM (M = methacrylate unit), AAM
and MAA, and AAA comonomer triads, respectively.
Based on the actual mole fraction of acrylonitrile and methyl acrylate
comonomers in the feed f1 and f2, respectively, the mole fraction of comonomers
expected in the copolymer F1 and F2, respectively, were calculated using zero-
(Bernoullian) and first-order Markov or terminal model probabilities. First order
probabilities were calculated using the following equations:
r1f12 + f1f2
F1 = and F1 = 1− F2 [81]
r1f12 + 2f1f2 + r2 f22
where r1 and r2 are the monomer reactivity ratios of the AN and MA comonomers,
whose instantaneous values are 1.5 and 0.84 respectively. For AN and vinyl
acetate (VA), the ratios are 5.5 and 0.06, respectively [81].
5.1.3 Differential Scanning Calorimetry (DSC)
A Perkin-Elmer Diamond 7 DSC instrument calibrated with indium and
zinc was used to collect thermograms. Specimens were vacuum-dried for four
days and prepared by cutting pellets into granules with a razor blade. They were
weighed and encapsulated in volatile aluminum pans. A cyclic procedure was
used with the multiple melting at successive heating rates of 5, 10, and 20º
C·min-1 from 25 to 250º C [82].
5.2 Results and Discussion
5.2.1 Solution 13C Nuclear Magnetic Resonance
Most high acrylonitrile content, flooded free radical PAN homo- and
copolymers are known not to exhibit a melting endotherm at low ramping heating
rates [55, 83, 84]. Eby [71] proposed a method of predicting melting
temperatures for copolymers that includes comonomers as defects in their
crystalline regions, which Frushour [74, 85-87] demonstrated is generally
applicable to free radical polyacrylonitrile copolymers. Inference of the melting
point was made from wet melting points obtained in high pressure DSC scans
when mixing two parts water with one part copolymer. For many co- and
terpolymers of acrylonitrile, Eby’s model in association with Frushour’s wet
melting point depression accurately describe and predict the dry melting behavior
for some common comonomers.
Frushour’s model describing melting behavior for copolymers is
dependent on the comonomer concentration and the molar volume of their
sidegroups. Methyl acrylate and vinyl acetate have similar molar volumes, 36
and 39 cm3·mol-1, respectively. No dry-polymer melting point depression
constant is reported for PAN copolymers including MA, as “many of the polymers
decomposed before the melting could be measured.” Yet for VA, Frushour
reports a different wet melting point depression constant than that observed by
Slade et al., in dry melting experiments, the former of which is similar to the wet-
polymer melting point depression constant for MA [88]. Since a dry melting
temperature depression constant was observed for VA and not MA another
aspect of copolymer structure must affect their melting behavior.
The number average acrylonitrile sequence lengths of AN/MA and AN/VA
copolymers with various compositions were predicted and are compared with
those observed in Table 3 and Figure 9. Flooded free radical PAN comonomer
sequence lengths are predicted using zero (Bernoullian), first (Terminal) and
second (Penultimate) order Markov models from comonomer composition,
comonomer reactivity ratios, and observations of free radical AN/MA copolymers
[1] and AN/VA copolymers [89] by Brar, et al. Actual sequence lengths in
commercial high PAN fibers were calculated using triad concentrations obtained
by integration of the Amlon® and Dralon® 13

C NMR spectra recorded in d6-
dimethylsulfoxide at 120º C, such as presented in Figure 8. The second order
model shows the most accurate prediction for the free radical AN/MA up to 88%
acrylonitrile, see Figure 9. Yet, the observed sequence length of AN units in
Dralon® shows a nearly discontinuous shift/increase. The sequence length more
accurately reflects that predicted by random Bernoullian probability.
Furthermore, for Amlon® D the average length of contiguous AN units is
approximately thirteen, which is over two times the flooded equivalent and three
times less than in Dralon®. The resulting Amlon® D structures have block lengths
of intermediate size, whose specific size may not be possible in a flooded
copolymerization that yields a 85% AN: 15% MA copolymer. Thus, BP’s
scavenged reaction may offer sequence control beyond that of the flooded
monomer reactivity.
While the molar volume of the monomers MA and VA are similar, their
reactivity ratios with AN are significantly different. When comparing the predicted
and observed AN sequence lengths with respective comonomers, the VA
copolymer shows a more alternating and less blocky structure, which is
emphasized when comparing their comonomer triad concentrations. The
Penultimate model also more accurately describes the sequence lengths for
AN/VA. However, observed molar compositions are only 61, 64 and 75% AN.
The Terminal model is shown to predict a somewhat longer sequence length in
both MA and VA copolymers. When comparing the respective predicted AN
sequence lengths, the AN sequence length for the MA copolymer is over two
times larger than for the VA copolymer at the same AN molar composition. This
longer theoretical sequence length would provide longer ‘crystallizable’ AN units
and could explain the difference in melting behavior that is observed in these
copolymers. This would further address why shrinkage is more prevalent in
some acrylonitrile copolymers at higher comonomer concentrations [4, 90, 91].
Insertion of MA and VA units into PAN likely increases the conformational
flexibility of the copolymer relative to the PAN homopolymer [92, 93]. This
increase in conformational flexibility would be greater in AN/VA copolymers,
because the VA units are more randomly inserted as compared to the more
blocky insertion of MA units in Amlon® D. As a consequence, for the same
comonomer content AN/VA copolymers would be expected to exhibit greater
shrinkage than the Amlon® D copolymers.
67
Table 3. Comonomer Distributions and Number Average Sequence Lengths for Methyl Acrylate and Vinyl Acetate Copolymers
Polymer Molar Acrylonitrile Triad Comonomer Triad Number Number
Markov Feed Ratio
Comonomer Composition Concentrations Concentration Average Average X
Model
FAN FX fAN fX AAA AAX XAX XXX XXA AXA AN Length Length
0.71 0.29 0.50 0.41 0.08 0.08 0.41 0.50 3.45 1.41
0.85 0.15 0.72 0.26 0.02 0.02 0.26 0.72 6.67 1.18
0 0.88 0.12 0.77 0.21 0.01 0.01 0.21 0.77 8.33 1.14
0.93 0.07 0.86 0.13 0.00 0.00 0.13 0.86 14.29 1.08
0.98 0.02 0.94 0.06 0.00 0.00 0.06 0.94 33.67 1.03
0.71 0.29 0.62 0.38 0.40 0.49 0.10 0.13 0.44 0.43 2.87 1.55
0.85 0.15 0.79 0.21 0.63 0.34 0.03 0.04 0.30 0.67 5.06 1.23
1 Methyl 0.88 0.12 0.83 0.17 0.70 0.28 0.02 0.03 0.25 0.73 6.18 1.18
Acrylate 0.93 0.07 0.90 0.10 0.81 0.18 0.01 0.01 0.16 0.83 10.17 1.10
0.98 0.02 0.97 0.03 0.94 0.06 0.00 0.00 0.05 0.95 33.99 1.03
0.71 [1] 0.29 0.46 0.43 0.11 0.01 0.19 0.79 3.33 1.14
2
0.88 [1] 0.12 0.70 0.28 0.03 0.00 0.10 0.90 5.94 1.05
0.71 [1] 0.29 0.50 0.40 0.10 0.02 0.19 0.79 3.33 1.13
0.85 0.15 Amlon® 0.86 0.12 0.02 0.08 0.15 0.77 13.10 1.19
Observed
0.88 [1] 0.12 0.67 0.28 0.05 0.00 0.14 0.86 5.26 0.67
0.93 0.07 Dralon® 0.95 0.04 0.00 0.00 0.00 1.00 39.04 1.00
0.40 0.60 0.16 0.48 0.36 0.36 0.48 0.16 2.38 1.73
0.50 0.50 0.25 0.50 0.25 0.25 0.50 0.25 4.33 1.30
0 0.70 0.30 0.49 0.42 0.09 0.09 0.42 0.49 6.83 1.17
0.85 0.15 0.72 0.26 0.02 0.02 0.26 0.72 13.14 1.08
0.98 0.02 0.90 0.10 0.00 0.00 0.10 0.90 33.67 1.03
0.79 0.21 0.41 0.59 0.23 0.68 0.09 0.01 0.02 0.97 2.31 1.02
0.85 0.15 0.51 0.49 0.32 0.62 0.06 0.01 0.01 0.98 2.73 1.01
1 Vinyl 0.93 0.07 0.71 0.29 0.54 0.45 0.02 0.00 0.00 0.99 4.18 1.00
Acetate 0.98 0.02 0.90 0.10 0.82 0.18 0.00 0.00 0.00 1.00 10.71 1.00
[89] 0.40 0.60 0.14 0.46 0.41 0.00 0.08 0.92 1.58 1.04
2 [89] 0.50 0.50 0.22 0.49 0.29 0.00 0.05 0.95 1.87 1.03
[89] 0.70 0.30 0.45 0.43 0.11 0.00 0.98 0.95 3.05 1.34
0.61 [89] 0.39 0.40 0.60 0.15 0.47 0.38 0.00 0.08 0.92 1.63 1.04
Observed 0.64 [89] 0.36 0.50 0.50 0.20 0.50 0.30 0.00 0.05 0.95 1.82 1.03
0.75 [89] 0.25 0.70 0.30 0.45 0.43 0.12 0.00 0.98 0.95 2.97 1.34
Acrylonitrile
Triads
MAA AAA
MAM
DMSO-d6
Intensity
120.5 120 119.5 119 118.5 118
AMA MMA Methyl acrylate

Triads
174 173 172 171
MA AN
0
200 175 150 125 100 75 50 25 0
ppm
Figure 8. Solution 13C NMR Spectra of Amlon® D in d6-DMSO
Length
45
Length
40
Sequence
Sequence 35
30 Dralon®
Amlon® D
25
ANAN
Zero-order
20
Average
First-order
Average
15
Second-order
10
Number
5
Number
Observed [1]
0
0 .3 0 .4 0 .5 0 .6 0 .7 0 .8 0 .9 1
Mole Fraction of AN
Figure 9. Number Average Acrylonitrile Sequence Length for Methyl

Acrylate Copolymers by Mole Fraction of Acrylonitrile: Observed Lengths
and Zero-Order, First-Order, and Second-Order Markov Models Lengths
5.2.2 Differential Scanning Calorimetry
For Amlon® D at a ramp rate of 20º C·min-1 (Figure 11), the melting
thermograms show a small endothermic peak at approximately 218º C, which is
higher than observed for a free radical copolymer with the same molar
composition and occurs below the onset of thermal degradation. The
intermediate blocky structure in Amlon® D produces less stable paracrystals than
Dralon®, but more stable than those in equivalent AN/VA copolymers, as
evidenced by the DSC scans.
When considering Amlon® D and its equivalent free radical copolymer, the
larger Amlon® D crystals would normally be expected to be more stable and
require a higher melting temperature compared to free radical PAN copolymers.
However, the lack of a discrete melting endotherm likely means that the PAN
crystals in Amlon® D are ‘nonequilibrium’, where segmental dipole interactions
dominate the combination of related torsional, steric and/or angular constraints
on the copolymer chains. In other words, since the acrylonitrile sidegroups have
such strong dipole moments, the strength of their interchain interactions
supersedes the forces that usually govern the equilibrium conformations of a
regular vinyl chain. As such, the disruption of these Amlon® D ‘crystal’ units may
be a transient process and not a first-order thermodynamic transition, whereby
increased thermal energy gradually disrupts individual dipole attractions sufficient
for melt-processing below the onset of AN degradation. Since the melting
thermogram shows no discrete endotherm, the as-crystallized polymer likely
transitions from a more nonequilibrium crystal into a less nonequilibrium structure
with increased heating. Furthermore, at a heating ramp rate of 5º C·min-1
Amlon® D shows no glass transition or melting endotherm, which indicates that
the ‘218º C transition’ observed at higher heating rates likely occurs over a
discrete and measurable amount of time, ie., is not a first-order phase transition
typical of the melting of semi-crystalline polymers.
The DSC scans show a polymer with some order, although not
traditionally crystalline. Thermograms are compared for polymers dried for zero
and four days in Table 4 and Figure 11. The presence of water generally lowers
the glass transition and ‘melting’ temperatures. Drying the polymer widens the
range of the peaks and enthalpies of crystallization. At a rate of 5º C·min.-1, a
fusion peak is not discernable. Only at higher rates do heating peaks emerge,
however, their source is not defined and they are difficult to measure [94].
None of the thermograms show a typical equilibrium melting endotherm,
see Figure 11 a) and c). At 20º C·min-1 a slight fusion peak emerges. This
nondescript profile is similar to that recorded by Illers’ on a 85:15 AN:MA free
radical copolymer [95]. However, at 5º C·min-1 Amlon® D shows essentially no
change in the baseline behavior. Clear ‘recrystallization’ exotherms suggest,
however, that reordering is occurring, see Figure 11 b) and d). Similar changes
in the area of ‘recrystallization’ exotherm by ramp rate are observed for
poly(ethylene terephthalate) fiber, Figure 10. The change in exotherm peak for
PET becomes broader with increased ramp rate. For Amlon® D, the peaks
become narrower and larger magnitude. This further suggests that a different
type of crystal structure is formed than observed in semi-crystalline polymers.
5.2.3 Conclusions
The present investigation provides a microstructural basis for the
difference in bulk behavior between Amlon® D and flooded PAN copolymers,
because the acrylonitrile run length in Amlon® D is significantly different. This
intermediate intrachain microstructure supports crystals that are able to be
disrupted and “melt” at a lower temperature, rendering it melt processable. Most
importantly, this length is sufficient to impart mechanical stability by preventing
significant shrinkage upon heating. The Amlon® D paracrystalline domains “melt”
in a nonequillibrium fashion, and indicate that PAN copolymer paracrystals
generally conform in a mesomorphic manner that exhibit no equilibrium first-order
phase transition, unlike most semi-crystalline vinyl homo- and copolymers.
5 ºC·min-1
Heat Flow (mW)
10 ºC·min-1
20 ºC·min-1
125 150 175 200 225 250

Temperature (C)
Figure 10. Differential Scanning Calorimetry Cooling Thermograms for

Poly(ethylene terephthalate) Tire Cord Fibers
Table 4. Thermogram Inflection Points and Enthalpies

for Dried and Undried Amlon® D Pellets
Scan Temperature Enthalpy
State Peak
(ºC·m-1) (ºC) (J/g)
Glass 83.01
5 Melting none
Crystallization 189.58 -6.911
Glass 82.29
undried 10 Melting 213.65
Glass 84.80
20 Melting 211.17
Glass 85.43 -
5 Melting 215.47 -
Glass 86.52 -
dried 10 Melting 218.22 -
Glass 87.58 -
20 Melting 218.44 -
.
.
20ºC·min-1
9
Heat Flow (mW)

7
10ºC·min-1
5
3
5ºC·min-1
1
.
.
.
50 75 100 125 150 175 200 225 250
Temperature (C)
. 5ºC·min-1
.
10ºC·min-1
Heat Flow (mW)
.
20ºC·min-1
.
.
.
150 160 170 180 190 200 210

Temperature (C)
Figure 11. Differential Scanning Calorimetry Thermograms for

Dried and Undried Amlon® D Pellet Thermograms
a) Dried melting.
b) Dried Crystallization.
.
.
20ºC·min-1
.
Heat Flow (mW)

.
. 10ºC·min-1
.
5ºC·min-1
.
.
.
.
50 75 100 125 150 175 200 225 250
Temperature (C)
.
5ºC·min-1
.
. 10ºC·min-1
Heat Flow (mW)
.
. 20ºC·min-1
.
.
.
150 160 170 180 190 200 210
Temperature (C)
Figure 11. Differential Scanning Calorimetry. (continued)
c) Undried Melting.
d) Undried Crystallization.
Polymer Thermomechanical Analyses 76
6 Polymer Thermomechanical Analyses
The ability of a polymer to be converted from chip to product requires that
it maintain stability over a range of conditions. The rheological and mechanical
response to temperature characterizes its behavior. In order to extrude a
thermoplastic material, the optimal processing conditions must be identified.
Hygroscopic behavior in polymers is a function of the availability of
electronegative sidegroups that provide a site to attract water molecules.
Hydrophilic commodity thermoplastic polymers are routinely dried before
processing to improve the mechanical integrity through order and orientation.
Polyamide, with a regain of 3.5 – 4.5%, and polyethylene terephthalate, with a
regain of 0.3 – 0.4%, are the typical examples [44].
Flooded high polyacrylonitrile is one of the standard precursors for carbon
fibers, as it readily degrades before any resemblance of melting behavior is
observed. During the manufacture of carbon fiber from PAN, various byproducts
degas and weight is lost as the chain structure and sidegroups crosslink, cyclize
and convert to carbon [47, 96].
Due to the complexity and toxicity of related processing technologies, the
number of studies published regarding polyacrylonitrile rheological data is limited.
Most of the publications concern solutions and gels [97-102]. One recent paper
[103] reports data on dynamic viscosity for a range of acrylonitrile to methyl
acrylate concentrations for copolymers it claims to have synthesized in a manner
similar to the Amlon® patents by British Petroleum [76, 104-108].
6.1 Experimental
The overall objective of the thermomechanical studies was to develop an
understanding of the basic behavior of the polymer in molten form. Vacuum
drying to evacuate moisture and ensure consistent extrudate conditioned Amlon®
D was used. Isorate thermogravimetric analyses reported the regimes of phase
transition as a function of pyrolysis and a general range of temperatures suitable
for melt processing. Isothermal thermogravimetric analyses provided a
quantitative assessment of the polymer stability at different temperatures. The
tandem mass spectrometry reported the byproducts of degradation as an
indication of its mechanism. As capillary rheometry is the original method of
assessing the flow behavior of thermoplastic polymers and since the shear rates
are similar to those found in industrial processes, it is the chosen method of
evaluating the effects of melt time and temperature on viscosity [109].
6.1.1 Drying
Since the regain of polyacrylonitrile is 1-2% [44], Amlon® D was dried at
120ºC from one to four days at 4 mm of Hg.
6.1.2 Fourier Transform Infrared Spectroscopy (FTIR)
A Thermo-Nicolet Nexus 470 FT-IR ESP with Avatar Omni-Sampler
attachment from Thermo Electron Corporation was used for the FTIR scan. The
scan was corrected with attenuated total reflectance. A sample was prepared by
slicing a pellet with a razor blade to produce a 1mg sample that was placed on
the crystal. Thirty-two scans were collected.
6.1.3 Thermal Gravimetric Analysis (TGA) & Mass Spectrometry (MS)
A TA Instruments TGA2950 of New Castle, Delaware was utilized for TGA
with a tandem MS from Pfeiffer Vacuum Instruments Model GSD 301 T. A
Perkin-Elmer Pyris 1 TGA calibrated with nickel and zinc was also utilized for
studies for high temperature degradation. For isothermal scans, the system was
purged with Argon 1 hour before and 30 minutes after loading a sample. The
temperature was ramped from ambient conditions to 200°C at 20°C·min-1. The
system was equilibrated at the melt temperatures listed in Table 6. It was held
for 2 hours while observing weight loss and degassed ions.
High temperature degradation studies were conducted in the presence of
air and nitrogen at ramp rate of 20°C·min-1 from 50ºC to 950ºC [110].
6.1.4 Capillary Rheometry
A Haake Rheoflixer HT type 556-0100 single bore capillary rheometer
from Thermo Electron Corporation was used. Round die dimensions and shear
rates are found in Table 5 and the entrance angle was 90º.
The range of recommended spinning temperatures was obtained from
internal British Petroleum laboratory data. Polymer melt stability was determined
through thermal gravimetric analysis with mass spectrometry. Final
temperatures and melt times were chosen based on a consistent extrudate.
These are shown in Table 6. Consistent polymer stream is one without defects
with similar viscosity curves. Collection methods were in accordance with ASTM
Standard D3835-02. Correction treatment and calculations based on standard
rheological procedures were performed.
Table 5. Capillary Rheometry: Die Dimensions and Shear Rates

Capillary
Length (mm) Diameter (mm) Shear Rate (s-1)
Die
1 10.0 2.0 10 – 2564
2 20.0 2.0 10 – 2564
3 30.0 2.0 10 – 2564
The Rheoflixer with mounted die was allowed to equilibrate at the desired
melt temperature. The single barrel was filled with dried polymer pellets. The
piston was attached and the head descended to contact the sample. Once a 12
bar pressure was reached, movement stopped and the polymer melt time began.
Once the melt time was reached, the sample was compressed for 60
seconds at 20 bar. Before extrusion, the pressure was decompressed to 10 bar
for 30 seconds. If the polymer flowed freely, shear rates began at 10 s-1 and
ended at 2564 s-1. Otherwise, if the polymer failed to exit the die at low shear
rates, shear sampling began at 2564 s-1 and ended at 10 s-1. Five data points
per shear rate 100 milliseconds apart were obtained once the piston pressure
stabilized at less than 2 bar·s-1.
The Bagley correction was calculated using pressure and apparent shear
rate, and L/R, where L is the die length and R is the die radius. True shear
stress was calculated using, σ R =

(∆P)R , where ∆P is the pressure change
2(L + e oR )
and eo is the end or Bagley correction [109]. The value was obtained as the y-
intercept of a linear fit between pressure and L/R.
Throughput Q was calculated using the relationship with apparent shear
4Q
rate γ& app = . The true shear rates were determined with the Rabinowitsch
πR 3
⎛ 3 1 dlnQ ⎞
procedure using the equation: γ& W = γ& app ⎜⎜ + ⋅ ⎟⎟ . True viscosity ηW was
⎝ 4 4 dlnσ R ⎠
σR
determined using η W = [109].
γ& W
Table 6. Extrusion Conditions: Melt Temperature and Melt Times
Material Temperature (ºC) Melt Times (min)

Amlon® D 210 25, 12, 9
Amlon® D 220 11, 5, 3
Amlon® D 230 7, 5, 3
6.2 Results and Discussion
6.2.1 Vacuum Drying
Batches of approximately 650 grams of polymer were vacuum dried.
Nearly 0.5% weight is lost after one day of drying, see Figure 12. On average
0.25% additional weight is lost during drying between days 2 and 4.
Given that the hydrophilic nature of these polymers is driven by hydrogen
bonding, water is both freely and weakly held in the bulk. The polar acrylonitrile
sidegroups in polyacrylonitrile provide sites of stronger attraction. Thus, it
requires additional time and energy to release the water bound there.
6.2.2 Chemical Composition
FTIR scans verify the contents of the polyacrylonitrile copolymerized with
methyl acrylate, see Figure 13. The 3350 cm-1 band shows residual water.
Methyl groups from the copolymer are indicated at 2920, 2850 and 1450 cm-1.
The acrylonitrile sidegroup is shown by the band at 2240 cm-1. Carbonyl groups
in methyl acrylate are shown by the 1730, 1650 and 1580 cm-1 bands. Thiols in
the mercaptan as well as ester links in the copolymer and/or maleate ester
stabilizer are indicated in peaks at 1230, 1170 and 1120 cm-1. Possible sulfate
residues from the initiator and surfactant are indicated with the 1120 cm-1 peak.
0.75
Weight Loss (%)

0.5
0.25
0 1 2 3 4
Day
Figure 12. Weight Loss during Vacuum Drying of Amlon® D Pellets
0.0125
2920
0.01
1650
1580
1730
1450
3350
Absorbance
0.0075
2850
1170
1120
1230
0.005
2240
0.0025
0
4000 3000 2000 1000
Wavelength (1/cm)
Figure 13. Fourier Transform Infrared Spectra of Amlon® D Pellets
6.2.3 Thermal Stability
The ability of the polymer to maintain stability for prolonged periods of time
under isothermal conditions is a requisite for commercial fiber spinning. Figure
14 shows the isothermal weight loss for Amlon® D vacuum dried 1 day at 120 ºC.
Higher temperatures show larger amounts of weight loss. The amount of loss is
approximately 0.50, 1.00, and 1.50 % for 210, 220 and 230 ºC, respectively. The
weight loss for the 220 ºC scan shows an inconsistency with the others. This
could be caused by material variability in the batch polymerization process.
Amlon® D pellets are clear and yellow, which is due to the typical yellow
color of acrylonitrile monomer. The color gradually changes to shades of orange
during heating as it crosslinks and blackens as it pyrolizes. After isothermal
treatment, the specimens exhibited different shapes and colors. The 210 ºC
sample remained clear and in pellet shape, but turned light orange. The 220 ºC
specimen formed an opaque amber colored amoeba shape with large bubbles.
The 230 ºC scan resulted in a blackened solid also having large bubbles. The
shape and color changes indicate varying degrees of melting and degradation.
The degradation stages for Amlon® D under nitrogen and air purge is
shown in Figure 15. For both scans, the onset inflection occurs at approximately
400 ºC. A second inflection under both purges occurs at between 500 and 525
ºC. The final weight is approximately 42% of the original. Under nitrogen
Amlon® D stabilizes at a lower weight, while in air no stabilization is reached.
Final weight is approximately 30% of the original. Oxidation reactions drive the
degradation. Thus, degradation of Amlon® D is sensitive to oxygen [111].
100
99.8
Weight fraction (%)

99.6
99.4
99.2
99
98.8
98.6
98.4
40 60 80 100 120 140 160 180 200 220 240
Temperature (C)
Figure 14. Quasi-Isothermal Stability Thermogravimetric Analyses

of Undried Amlon® Pellets.
100
Weight Fraction (%)
75
air
50
nitrogen
25
0 250 500 750 1000
Temperature (C)
Figure 15. Isorate Degradation Thermogravimetric Analyses

of Undried Amlon® Pellets.
6.2.4 Degradation Byproducts
The mass spectrometry data shows the products of degradation over the
duration of the scans, see Figure 16. Data is presented with mass fraction on the
x-axis as the scans were taken at isothermal temperatures for 2 hours
concurrently with TGA. Ions with maximum relative intensity measured in mass
over charge (m/e) above 1% include 17, 18, 20, 28, and 40. Tests for unequal
variances showed only ion 28 with a statistically similar data spread.
The composition of the polyacrylonitrile copolymerized with methyl
acrylate support ion composition including carbon, hydrogen, oxygen and
nitrogen. These are likely to be present in the form of water as well as monomer
and oligomer from the polymer and copolymer. Ion 17 corresponds to OH and
NH3. Ion 18 indicates H2O and NH4. CH2CN is shown by ion 20. Fragment 28
includes C2H4, CO, N2 and HCNH. Finally, ion 40 reflects C3H4 and CH2CN.
Changes in the trends of relative intensity are similar for ions 17 and 18.
Intensities for these curves are also comparable. As the material was dried only
for one day the loss of water is consistent with additional weight loss upon drying
for additional days.
Ions 20 and 40 also have similar trends in the change of relative intensity.
The scan at 230ºC shows consistently high emissions with no clear equilibrium
reached. Temperatures 210ºC and 220ºC show smaller intensities, then taper off
quicker. With an inflection point near the end of the scan, the lower two
temperatures reach a quasi-equilibrium state.
Interestingly, the 230ºC scan shows lower amounts of ions 17 and 18 and
larger sustained amounts of ions 20 and 40. At temperatures 210 and 220ºC, ion
20 begins with the same intensity and tapers off gradually. A similar trend is
observed for ion 40. However, for the latter ion, all three scans originate with the
maximum intensity [112].
Given the chemical composition of the acrylonitrile co-methyl acrylate
copolymer, the ions detected during degradation at the three melt temperatures
are expected. The source of these ions as it relates to the stability of the
molecular weight cannot be determined. Size exclusion chromatography of
samples heated for long periods of time will indicate the mechanism of
degradation, whether detrimental chain scission or a negligible lowering through
a removal of end units or unreacted comonomers. In general, stability of Amlon®
D over prolonged exposures to elevated temperatures becomes a factor in a
processing operation only when the supply of molten polymer fails to be
delivered in a consistent manner. In other words, if not dealt with properly, zones
of low or no flow rate may lead to defective or low performance extrudate.
6.2.5 Melt Time
Limits to melt (dwell) time were determined empirically. Isothermal TGA
analyses provided insight into the relative weight loss by temperature. The lower
limit was determined once evidence of melt fracture disappeared [109].
Sharkskin was prevalent at low relative dwell times and high shear rates, see
Figure 17.
Upper limits were determined from air bubbles. Different sizes and
placements of bubbles were observed. Large air bubbles were observed if
insufficient air evacuation or packing occurred. These are shown across the
entire melt diameter, wholly within the melt and on the surface of the melt. For
consistent, defect-free extrudate, care must be taken to properly pack pellets in
the capillary bore. Small bubbles are evident in insufficiently dried polymer for
polymers treated over exceedingly long dwell times. These bubbles are caused
by water vapor or gaseous products of degradation.
0.05
0.04
m/e 17; NH3,OH
0.03
0.02
0.01
98.5 98.75 99 99.25 99.5 99.75 100
Mass Fraction (%)
210ºC
220ºC
230ºC
Figure 16. Mass Spectrometry Fragments of Undried Amlon® D Pellets

Collected with Tandem Isothermal Thermogravimetric Analyses.
a) m/e 17.
0.175
0.15
m/e 18; H2O

0.125
0.1
0.075
0.05
98.5 98.75 99 99.25 99.5 99.75 100
Mass Fraction (%)
0.23
0.22
0.21
CH2CN
0.2
0.19
0.18
98.5 98.75 99 99.25 99.5 99.75 100
Mass Fraction (%)
210ºC
220ºC
230ºC
Figure 16. Mass Spectrometry Fragments. (continued)
b) m/e 18.
b) m/e 20.
0.025
0.02
N2,C2H4,CO,HCNH
0.015
0.01
0.005
98.5 98.75 99 99.25 99.5 99.75 100
Mass Fraction (%)
0.95
C3H4,CH2CN
0.9
210ºC
220ºC
0.85 230ºC
0.8
98.5 98.75 99 99.25 99.5 99.75 100
Mass Fraction (%)
210ºC
220ºC
230ºC
Figure 16. Mass Spectrometry Fragments. (continued)
c) m/e 28.
d) m/e 40.
6.2.6 Capillary Rheometry
The polymer was first run undried at 220ºC, shown in Figure 18b. As
expected, water acts as a lubricant and reduces the viscosity. However, the
values of the apparent viscosity fluctuated. Small and large bubbles were readily
visible in the extrudate, Figure 17.
Consistent extrudate was obtained with polymer that was vacuum dried for
two days. The temperature effect on the viscosity of Amlon® D is clearly
illustrated in Figure 18a through 17c. True viscosity and true shear rate is
calculated by the ratio of die length to diameter using data from all dwell times.
The curves show nearly identical agreement between dwell times and L/D.
Viscosity decreases with increase in melt temperature and shear rate. The flow
supports the power law showing the relation between true shear stress and true
n
shear rate: σ R = m γ& R where m is consistency and n represents the power-law
index. Linear fit values are shown in Table 7.
Table 7. Power Law Index for Dried Amlon® D Capillary Rheometry
Temperature (ºC) Index (n)
210 0.3861
220 0.5122
230 0.6698
For comparison, polypropylene was run at 180ºC and its melt viscosity
behavior is shown in Figure 18d). At low shear rates, the viscosity is similar to
Amlon D at 230ºC. At high shear rates, the viscosity is lower.
6.2.7 Conclusions
The basic thermal properties and rheological behavior of Amlon® D for
fiber spinning are reported. Prior to processing, drying was found essential. The
polymer is concluded to be pseudo-crystalline in bulk without defined glass or
melting peaks. However, crystallization, or reordering peaks are distinct. Quasi-
isothermal TGA analysis shows that the polymer is more stable at lower
temperatures. Isorate TGAs demonstrate that the polymer decomposes to a
stable carbonaceous material at high temperatures under inert conditions. Mass
spectrometry shows that the products of degradation are expected to be water,
monomers and oligomers. The rheological behavior of the molten polymer
follows the power law relation. A stable extrudate is observed under a range of
dwell times and temperatures. At high temperatures, the viscosity decreases
and the behavior is similar to polypropylene.
The results of the thermomechanical study provided the evidence to
support selection of a melt processing condition – 220ºC for a melt time of 5
minutes. This choice was made from the observation of stability as a function of
melt time. At 220ºC, the polymer could be melted relatively quickly with almost
negligible loss of weight.
Figure 17. Melt fractures of Dried Amlon® D Extrudate

from Capillary Rheometer
a) 7.5X Sharkskin, 220ºC melt temperature and 3 minute dwell time.

b) 7.5X Bubbles, 230ºC melt temperature and 12 minute dwell time.
1e5
1e4
True Viscosity (Pa s) 1e3
100
10
10 100 1e3 1e4 1e5
True Shear Rate (1/s)
1e5
1e4
True Viscosity (Pa s)
dried
1e3
undried
100
10
10 100 1e3 1e4 1e5
Figure 18. True Viscosities by True Shear Rate for Dried and Undried
Amlon® D and Polypropylene by Temperature and Melt Time
a) at 210ºC.
b) at 220ºC.
1e5
1e4

1e3
100
10
10 100 1e3 1e4 1e5
1e5
1e4
1e3
100
10
10 100 1e3 1e4 1e5
Figure 18. True Viscosities by True Shear Rate. (continued)
c) at 230ºC.
d) Polypropylene at 180ºC.
Melt Extrusion 95
7 Melt Extrusion
The objective of the continuous fiber spinning study was to obtain an
indication of the achievable fiber properties and to identify potential optimal
parameters that should be investigated further at a later date. Fiber properties
produced by melt extrusion are generally dependent upon such physical
characteristics as crystallinity, molecular weight and chain orientation. The
following discussion regarding mechanical properties of fibers is confined to
semi-crystalline polymeric materials. In determining the fiber properties from a
given resin molecular weight can be considered as an independent variable, if
the polymer chains are stable during conversion to fibers. So chain orientation
becomes the most important extrusion factor in maximizing the fiber properties.
A number of continuous processing conditions allow orientation
enhancement. Some of the most prominent methods include a heated shroud,
step drawings, and steam drawing. A shroud heated to a temperature between
the glass and melting transition points extends the amount of time that the chains
have to disentangle and orient. A stepped drawing zone enables property
enhancements through stages by minimizing the tension placed on the fiber for
draw. Roll temperatures also play an important role in thermoplastic materials by
influencing the amount of plastic deformation, which is generally material
specific. Steam, especially for acrylic fibers, where paracrystallinity is driven by
the interactions between acrylonitrile sidegroups, imparts additional chain
Melt Extrusion 96
mobility through decoupling. A recent paper investigated the achievable Amlon®
fiber properties for stepped and steam drawing [113].
Draw ratio is often given as the ratio of draw roller and take-up speeds.
However, drawing also occurs between the spinneret and take-up roller.
Mechanical properties are thus analyzed at different stages of drawing – drawing
between the extruder and the winding roller (spin-draw ratio) and drawing
between the two heated draw rollers (draw ratio). Spin draw is affected by the
length of time the extrudate remains molten after exiting the die, which is in turn
dependent upon the rate of heat transfer. The point at which the molten polymer
stream solidifies is called the solidification point. During this phase, the change
in the radius can be significant, especially if the solidification point is delayed with
a heat shroud. The heat shroud slows the rate of heat loss from the fiber stream,
enables smaller diameter formation, and generally allows chains to orient more
fully along the axis of the fiber. A high amount of orientation is generally not
achieved through winding unless high speeds (> 2500m·min-1) are used.
Partially-oriented fibers are thus generally considered as the product of the
winding zone in melt extrusion [9].
Post spin-drawing imparts further chain orientation and mechanical fiber
enhancements through deformation due to an elongation that induces a stress.
True stress is defined as the ratio of force to final cross-sectional area.
Conventional stress, used to characterize fibers, is the ratio of force to original
cross-sectional area. The three main types of deformation are: 1) plastic fracture
where stress plateaus and breaks, 2) deformation strengthening and 3) neck-
Melt Extrusion 97
type deformation. Solution-spun acrylic fibers exhibit deformation strengthening
behavior before reaching a maximum draw ratio. With the aid of steam as a
lubricant, it can undergo a neck-type deformation [9]. Most melt-spun fibers
exhibit a neck-type deformation where the fiber yields at a specific stress and
maintains a constant value while it irreversibly elongates. At a point (sometimes
called the natural draw ratio), which is dependent upon the material, dimensions
and elongation rate, the fiber strengthens as it deforms. Fibers are generally
drawn through the natural draw ratio for end-use application.
Draw ratios are imparted with and without the assistance of an external
heat source. In ‘cold-drawing,’ co-existent drawn and undrawn sections that
correspond to variation in fiber diameter characterize the behavior. The extent of
draw ratio depends on the material, rate of elongation and molecular weight.
Major commodity fiber-forming thermoplastics, such as polypropylene, polyamide
and polyethylene terephthalate, behave in this way. The temperature at which
this process is conducted is usually below the glass transition. The elongation
exhibited in these types of materials can range between 100-1000%. In ‘heated-
drawing’, the cross-sectional morphology is uniform and homogeneous.
Temperatures well above glass transition are used to impart a plastic
deformation without a distinct yield. A different history of temperatures between
glass and melting transitions yield different results [114].
The type and magnitude of drawing have long been used as the
independent variables in characterizing the mechanical properties of fibers. The
effects of draw ratio in the two drawing zones – winding draw and draw ratio –
Melt Extrusion 98
will be analyzed. Draw ratio will be presented as a ratio of initial to final fiber
diameters and by a ratio of drawing roller speeds. The fiber diameter was
calculated using an estimation of density, based on the reported density of the
PAN homopolymer, 1.17-1.19 g·cm-3 [44]. As the density of the methyl acrylate
comonomer is 1.22 g·cm-3, an estimated density for Amlon® D of 1.20 g·cm-3 was
used. The total effective draw ratio will also be used to correlate properties and
is hence defined as,
extrudate radius
total effective draw ratio = .
final fiber radius
7.1 Experimental
7.1.1 Extrusion Device
A single bore melt extrusion device, shown in Figure 19, was used to
extrude a monofilament by varying throughput, windup speed and draw ratio. A
round die of 2.0mm diameter and length of 30.0 mm was used. A pressure
transducer was mounted on the piston base and a temperature transducer was
mounted in the top of the die.
The bore was loaded with pellets that had been dried for 4 days. The
pellets were melted for at least 5 minutes at 220ºC. After this time, the polymer
was forcefully compressed to evacuate air. If air bubbles were present in the
extrudate, a high occurrence of fiber breaks occurred which prevented collection
of a sample of sufficient size without defects. During the compression, the
Melt Extrusion 99
polymer exhibited stick-slip behavior resulting in release of audible noises. As
the piston descended, the pressure first increased to 1400 and 1500 kg·force and
then released or slipped. Afterwards, the pressure fell to between 1100 and
1200 kg·force. Then it built up to a threshold and released again and again. This
irregular cyclic buildup and release occurred with less severity under low piston
speeds. As the polymer began to melt, the piston lowered more regularly until a
constant pressure level was reached where stick-slip behavior was no longer
observed. After 5 minutes, the sample was decompressed to 1100 kg·force for
approximately 30 seconds. Then the piston speed was set to the desired
nominal throughput rates.
Often times, the polymer required an additional 20-30 minutes before the
pressure stabilized. The stick-slip behavior gradually diminished and finally
disappeared once the piston emptied at least half of the bore. This behavior is
attributed to the bore design, which melts the pellets in the final 2 inches where
the die is heated by the jacket. A frictionless coating inside the bore and/or pipes
may reduce this phenomenon. A stable pressure regime ranged between 1100
and 1250 kg·force depending on the piston speed.
The piston speeds, a direct measure of throughput, was varied at 1.25, 2.5
and 5 mm·min-1. Once the pressure stabilized, the fiber was collected at speeds
varying from 100 to 750 m·min-1 and drawn inline between two draw rollers
heated at 110 and 125ºC. In later trials, an external heat source set at 145ºC
installed just below the exit of the orifice was used to reduce the quenching
gradient and quench point. The fibers were collected in a bag using an aspirator.
Melt Extrusion 100
Fibers were successfully spun at all throughputs. However, larger flow
rates required higher-than-available winding and drawing speeds to achieve
deniers under 50. A piston speed of 1.25 mm·min-1 was chosen as the setting
because the maximum take-up speed was the limit of achievable spin draw
ratios. A set of winding and drawing speeds were chosen and samples were
collected for 5 minutes without a break. For a piston speed of 1.25 mm·min-1, the
settings are shown in Table 8.
Table 8. Melt Extrusion, Winding and Drawing Conditions

Shroud Winding Roll Drawing Roll Drawing Roll
Temperature Speed Speed Draw Ratio,
( ºC ) ( m·s-1 ) ( m·s-1 ) by Speed
0 100 100 0.00
0 100 200 1.00
0 100 300 2.00
0 100 400 3.00
145 100 100 0.00
145 100 200 1.00
145 100 300 2.00
145 100 400 3.00
145 200 200 0.00
145 200 300 0.50
145 200 400 1.00
145 200 500 1.50
145 200 600 2.00
145 300 300 0.00
145 300 400 0.33
145 300 500 0.66
145 400 400 0.00
145 400 500 0.25
145 400 600 0.50
145 500 500 0.00
145 500 600 0.20
145 600 600 0.00
145 600 700 0.16
145 700 700 0.00
Melt Extrusion 101
Crank
Speed
Piston
Pressure
Capillary
Temp.
Extruder
Aspirator
& bag
12’
Drawing roll
Drawing roll (heated)
(heated)
Winding roll
9”
Bore
Spinneret
2”
Heated jacket
4”
Shroud
Extrudate
Figure 19. Melt Extrusion Device with Detail of Bore and Shroud Setup
a) extruder and windup unit

b) capillary extruder detail
Melt Extrusion 102
7.1.2 Mechanical Properties
The fibers were allowed to condition overnight at 25ºC and 65% relative
humidity. The denier and mechanical properties were measured on fibers with
gauge length of 2.54 cm in accordance with ASTM Standard 3288 using a
Favimat, Textechno, Mödchengladbach, Germany, and a cross-head speed of
200 mm·min-1. Data for the force at break or tenacity and elongation at break for
ten fiber specimens were collected for each sample. Cross section shape and
diameter variation were recorded optically.
7.1.3 Size Exclusion Chromatography
A Waters 1525 binary high pressure liquid chromatography pump with a
Waters 2414 refractive index detector, Milford, Massachusetts, was used to
obtain chromatograms corresponding to the molecular weight of fiber samples.
The column was a single Polymer Labs PLgel, 5µm particle size, mixed-d pore
type, 300x7.5mm column with a flow rate of 1 ml·min-1. The column was heated
to 50ºC and the detector to 30ºC. A solution of 0.01M LiBr-N,N-dimethyl
formamide was mixed and used as the mobile phase [115].
Polytetrafluoroethylene syringe filters, solvent filters and coated vials were used
with all samples. Each sample was injected separately.
7.1.4 Wide Angle X-ray Diffraction
Wide angle x-ray diffraction scans were collected on a diffractometer
instrument using Cu Kα radiation from Omni Scientific Instruments, Inc. of Biloxi,
Melt Extrusion 103
MS. The voltage was set to 40 milli-volts and the current was set to 30 milli-
amperes. Reflection scans were collected from fibers approximately one-inch in
length between 2θ angles of 10 to 35º in steps of 0.1º with a count time of 5
seconds. Transmission patterns were collected from fibers of one-half-inch that
were mounted horizontally on Polaroid Type 57 film.
7.1.5 Differential Scanning Calorimetry (DSC)
A Perkin-Elmer Diamond 7 DSC instrument from EG&G, Wellesley, MA,
calibrated with indium and zinc, was used to collect thermograms. Fiber
specimens were conditioned at 25ºC and 65% relative humidity. Melt extrusion
conditions are given in Table 8. Approximately 2.5 – 3.5 mg of fiber was rolled
into a ball and sealed in volatile aluminum pans. All samples were successively
heated and cooled at 30ºC·min-1 in the scan range of 50 to 250ºC [82].
7.2 Results & Discussion
7.2.1 Melt Spinning
The throughput setting at 1.25 mm·min-1 provided a wide range of draw
ratios. These settings provided a basis for comparing the effect of an auxiliary
heat shroud and draw ratio on the tenacity and elongation at break. Using low
variation in the denier of the fibers as a criterion (Figure 20 and Table 9), the
extrusion was considered acceptable as the material behaved in a manner
similar to that of other thermoplastic fibers.
104
Table 9. Tenacity and Elongation for Meltspun Amlon® D Fibers by Total Effective Draw Ratio
Winding Drawing Mean Draw Draw
Shroud Spin
Roll Roll Total Ratio, Ratio, Linear Density Tenacity Elongation
Temperature Draw
Speed Speed Draw by by ( denier ) ( gf·den-1 ) (%)
( ºC ) Ratio
( m·s-1 ) ( m·s-1 ) Ratio Diameter Speed
0 100 100 5.35 5.35 0.00 0.00 26.18 ± 1.58 2.27 ± 0.22 31.96 ± 10.48
0 100 200 5.99 5.35 0.64 1.00 16.61 ± 0.43 3.83 ± 0.44 26.58 ± 2.37
0 100 300 6.38 5.35 1.03 2.00 12.93 ± 0.23 3.86 ± 0.47 22.03 ± 1.61
0 100 400 6.54 5.35 1.19 3.00 11.74 ± 0.75 4.07 ± 0.92 21.81 ± 2.22
145 100 100 5.31 5.31 0.00 0.00 26.98 ± 1.57 2.28 ± 0.20 58.56 ± 11.38
145 100 200 6.30 5.31 0.99 1.00 13.62 ± 1.59 4.26 ± 0.52 29.34 ± 3.42
145 100 300 6.75 5.31 1.44 2.00 10.29 ± 0.34 4.78 ± 0.62 23.96 ± 2.30
145 100 400 7.23 5.31 1.92 3.00 8.01 ± 1.80 5.80 ± 0.81 21.73 ± 2.74
145 200 200 5.94 5.94 0.00 0.00 17.21 ± 0.25 2.26 ± 0.21 31.71 ± 3.91
145 200 300 6.57 5.94 0.63 0.50 11.63 ± 1.74 4.02 ± 0.63 31.21 ± 4.88
145 200 400 6.78 5.94 0.84 1.00 9.66 ± 0.61 4.12 ± 0.75 24.49 ± 3.46
145 200 500 6.90 5.94 0.96 1.50 9.44 ± 0.22 4.36 ± 0.66 23.52 ± 1.89
145 200 600 7.64 5.94 1.70 2.00 6.28 ± 0.34 4.90 ± 0.92 20.67 ± 2.37
145 300 300 6.36 6.36 0.00 0.00 13.05 ± 0.24 2.24 ± 0.19 28.42 ± 3.88
145 300 400 7.16 6.36 0.80 0.33 8.16 ± 0.68 3.90 ± 0.33 22.91 ± 1.53
145 300 500 7.39 6.36 1.03 0.67 7.20 ± 0.81 4.38 ± 0.41 23.28 ± 1.91
145 400 400 6.95 6.95 0.00 0.00 9.20 ± 0.91 3.12 ± 0.24 21.09 ± 1.06
145 400 500 6.96 6.95 0.01 0.25 10.40 ± 0.22 3.05 ± 0.20 22.70 ± 1.91
145 400 600 7.24 6.95 0.29 0.50 7.83 ± 0.57 3.54 ± 0.44 21.33 ± 1.68
145 500 500 7.20 7.20 0.00 0.00 7.97 ± 0.26 3.34 ± 0.21 22.61 ± 1.66
145 500 600 7.32 7.20 0.12 0.20 7.48 ± 0.82 3.54 ± 0.42 20.53 ± 2.34
145 600 600 7.37 7.37 0.00 0.00 6.92 ± 1.65 3.57 ± 0.55 24.22 ± 7.11
145 600 700 7.43 7.37 0.06 0.17 7.05 ± 0.66 3.68 ± 0.41 22.49 ± 1.54
145 700 700 7.73 7.73 0.00 0.00 6.02 ± 0.61 3.64 ± 0.30 21.80 ± 1.20
Melt Extrusion 105
7.2.2 Mechanical Properties
Solution processed acrylic fiber is formed during a collapse of the spin
dope during the diffusion of the solvent [5, 7]. This creates structures having
scales and voids within the fiber itself as well as an irregular fiber surface. Weak
points through these defects are created that reduce the tenacity of the fiber.
Nearly all acrylic fiber commercially produced is therefore in a staple form [5,
116]. Melt processable fibers are widely know to have more regular surfaces and
diameters, which was verified for Amlon® [117]. With fewer defects, higher
tenacities are expected. Furthermore, while solution-spun fibers exhibit a
deformation strengthening response to elongation [9], fibers from Amlon® D with
a low spin draw ratio exhibited plastic deformation (Figure 21). Fibers with a
larger total draw ratio exhibited a deformation strengthening behavior, whose
load increases with elongation.
Fibers first wound without a heat shroud at 100 m·min-1 are considered the
control. Fibers extruded and wound at 100 m·min-1 with and without the shroud
showed similar linear densities and tenacities, Table 9. However, the elongation
of the fiber extruded with the heat shroud is almost twice as large. The shroud,
in this case, most likely acts to allow the molecular chains to reach higher
orientation as entanglements, generally considered to hinder the degree of
elongation and loosened up. Drawn to the same ratio, the fiber with the shroud
had equivalent elongation, lower linear density, and higher tenacity. While the
final total draw ratio of both fibers wound at 100 m·min-1 is similar, the tenacity of
Melt Extrusion 106
the fiber with the heat shroud was nearly twice as large as that of Dralon®, 5.80
gf·den-1 compared with 3.11 gf·den-1.
The tenacity of the fibers was investigated as a function the spin draw
ratio, draw ratio, and total effective draw ratio. Figure 22 shows the distribution
of tenacities for the total draw ratio. The scatter plot, in general, demonstrates an
increasing linear trend in tenacity with an increase in total draw ratio, with an
overall mean tenacity of 3.70 gf·den-1. Elongation in Figure 23 shows a
decreasing trend with increasing total draw ratio, with an overall average of 26%.
The two largest tenacities are shown by fibers which had the highest draw ratio,
or by fibers extruded with the heat shroud wound at 100 and 200 m·min-1 and
drawn to 400 and 600 m·min-1, respectively. Nearly all Amlon® D fibers showed
greater tenacities than Dralon®.
When examining fiber tenacities as a function of spin draw ratio or draw
ratio, it is clearly observed in Figure 24 and Table 9 that a larger draw ratio yields
higher tenacity fibers. The plot of tenacity against spin draw ratio shows a wide
range of tenacity values for fibers with the lowest winding speed, 100 m·min-1,
regardless of the draw ratio. As the winding speed increases, up to a speed of
700 m·min-1, the average tenacity decreases. Figure 24 illustrates that
regardless of whether a shroud is present, higher tenacities are achieved through
higher draw ratio. When examining tenacities as a function of draw ratios, the
fibers extruded with the aid of the shroud show a larger draw ratio, smaller denier
and higher tenacity than those without a shroud. Values of tenacity are spread
Melt Extrusion 107
more evenly when plotted against versus draw value calculated from the ratio of
diameters rather than roll speeds.
A similar trend in elongation behavior is observed when it is examined as
a function of spin draw ratio and draw ratio, see Figure 26 and Table 9.
Elongation and variation in it both decrease as the spin draw ratio increases. As
draw increases, regardless of whether a shroud is used, the elongation
decreases. Higher variation in elongation is seen in the fibers with the lowest
and the highest draw ratios. Low draw ratios would be expected to induce
variation in elongation if the polymer chains were disorderly arranged or had
paracrystallized in a locally-entangled manner. Highest draw ratios would most
likely induce variation in elongation from the amplified effects of diameter
inconsistencies in small denier fibers or high tensions that induce weak points.
7.2.3 Molecular Weight
The retention time of the samples is an indirect measure of molecular
weight and is useful in gauging relatively changes in molecular weights. In this
case, any changes in molecular weight during extrusion would be noted by large
changes in retention times (Table 10). Fiber samples were selected to
incorporate a range of processing conditions and draw ratios. No significant
change in retention time is observed for the samples. No substantial change in
molecular weight is observed, which indicates that the polymer is stable from
pellet to fiber in a simple melt extrusion device.
Melt Extrusion 108
Table 10. Size Exclusion Chromatography Retention Times for

Amlon® D Fibers
Shroud Winding Roll Drawing
Mean Total Retention
Temperature Speed Roll Speed
Draw Ratio Time (min)
( ºC ) ( m·s-1 ) ( m·s-1 )
0 100 100 5.35 5.689
0 100 400 6.54 5.736
145 100 100 5.31 5.737
145 100 400 7.23 5.714
145 200 500 6.90 5.737
145 300 300 6.36 5.720
145 300 400 7.16 5.728
145 400 400 6.95 5.725
145 400 500 6.96 5.731
145 500 500 7.20 5.747
145 600 600 7.37 5.743
145 700 700 7.73 5.750
Melt Extrusion 109
35
30
Linear Density (den)

25
Average Total
Effective Draw Ratio
20
5.31
15
5.35
10 5.94
5.99
5 6.3
5 5.5 6 6.5 7 7.5 8
6.36
Total Effective Draw Ratio
6.38
6.54
35 6.57
6.75
6.78
30 8
6.9
6.95
Linear Density (den)
6.96
25
7.16
7.2
20 7.23
7.24
7.32
15 7.37
7.39
7.43
10
7.64
7.73
5
5 5.5 6 6.5 7 7.5 8
Average Total Effective Draw Ratio
Figure 20. Linear Density (denier) of Melt-spun Amlon® D Fiber

by Average Total Effective Draw Ratio
a) by Total Effective Draw Ratio

b) by Average Total Effective Draw Ratio
Melt Extrusion 110
50
40
30
Load (gf)
20
10
0 10 20 30 40 50
Elongation (%)
50
40
30
Load (gf)
20
10
0 10 20 30 40 50
Elongation (%)
Figure 21. Load by Elongation Curves for Amlon® D Fiber, Plastic

Deformation and Deformation Strengthening
a) Shroud, Wind Speed = 100 m·min-1, Draw Speed = 100 m·min-1

b) Shroud, Wind Speed = 100 m·min-1, Draw Speed = 400 m·min-1
Melt Extrusion 111
6
Average Total
Tenacity (gf / den)

5 Effective Draw Ratio
5.31
4 5.35
5.94
3 5.99
6.3
2 6.36
6.38
5 5.5 6 6.5 7 7.5 8 6.54
Total Effective Draw Ratio 6.57
6.75
6.78
8
6.9
7
6.95
6.96
6
7.16
Tenacity (gf / den)
7.2
5 7.23
7.24
4 7.32
7.37
3 7.39
7.43
2 7.64
7.73
5 5.5 6 6.5 7 7.5 8
Figure 22. Tenacity for Amlon® D Fiber by Total Effective Draw Ratio

b) Averaged by Extrusion Setting
Melt Extrusion 112
80
70
60 Average Total
Elongation (%)
50
5.31
40 5.35
5.94
30 5.99
6.3
20 6.36
6.38
5 5.5 6 6.5 7 7.5 8 6.54
6.75
6.78
8
7 6.9
6.95
6 6.96
7.16
Tenacity (gf / den)
5 7.2
7.23
4 7.24
7.32
7.37
3
7.39
7.43
2
7.64
7.73
5 5.5 6 6.5 7 7.5 8
Figure 23. Elongations for Amlon® D Fiber

by Average Total Effective Draw Ratio.

b) Averaged by Extrusion Setting
Melt Extrusion 113
6
Average Total
Tenacity (gf / den)

5.31
4
5.35
5.94
3
5.99
6.3
2 6.36
6.38
1 6.54
10 20 30 40 50 60 70 80
6.57
Elongation (%) 6.75
6.78
8
6.9
7
6.95
6.96
6
7.16
Tenacity (gf / den)
7.2
5
7.23
4 7.24
7.32
3 7.37
7.39
2 7.43
7.64
1 7.73
5 5.5 6 6.5 7 7.5 8
Spin Draw Ratio
Figure 24. Tenacity by Elongation and Spin Draw Ratio for Amlon® D Fiber
by Spin Draw Ratio.
a) by Elongation
b) by Spin Draw Ratio
Melt Extrusion 114
6
Average Total
Tenacity (gf / den)

5.31
4
5.35
5.94
3
5.99
6.3
2
6.36
6.38
1
0 .25 .5 .75 1 1.25 1.5 1.75 2 6.54
6.57
Draw Ratio, by Diameter
6.75
6.78
8
6.9
7
6.95
6.96
6
7.16
Tenacity (gf / den)
7.2
5
7.23
7.24
4
7.32
7.37
3
7.39
7.43
2
7.64
1 7.73
0 .25 .5 .75 1 1.25 1.5 1.75 2
Figure 25. Tenacities by Draw Ratio for Amlon® D Fiber

by Diameter Draw and Speed Draw Ratios.
a) No shroud. Draw is a ratio of initial to final fiber diameter.

b) Shroud at 145ºC. Draw is a ratio of initial to final fiber diameter.
Melt Extrusion 115
6
Average Total
Tenacity (gf / den)

5.31
4
5.35
5.94
3
5.99
6.3
2
6.36
6.38
1
0 .5 1 1.5 2 2.5 3 6.54
6.57
Draw Ratio, by Speed
6.75
6.78
8
6.9
7 6.95
6.96
6 7.16
7.2
Tenacity (gf / den)
5 7.23
7.24
4 7.32
7.37
3 7.39
7.43
2 7.64
7.73
1
0 .5 1 1.5 2 2.5 3
Figure 25. Tenacities by Draw Ratio. (continued)
c) No shroud. Draw is a ratio of final to initial roller speeds.

d) Shroud at 145ºC. Draw is a ratio of final to initial roller speeds.
Melt Extrusion 116
80
70
Average Total
Elongation (%) 50 5.31
5.35
40 5.94
5.99
30 6.3
6.36
20
6.38
10 6.54
5 5.5 6 6.5 7 7.5 8 6.57
Spin Draw Ratio 6.75
6.78
8
6.9
Figure 26. Elongations at Break for Amlon® D Fiber 6.95
6.96
7.16
by Spin Draw Ratio.
7.2
7.23
7.24
7.32
7.37
7.39
7.43
7.64
7.73
Melt Extrusion 117
80
70
60
Average Total
Elongation (%)
50
5.31
40 5.35
5.94
30
5.99
20 6.3
6.36
10 6.38
0 .25 .5 .75 1 1.25 1.5 1.75 2 6.54
Draw Ratio, by Diameter 6.57
6.75
6.78
8
80 6.9
6.95
70 6.96
7.16
60
7.2
Elongation (%)
50 7.23
7.24
40 7.32
7.37
30 7.39
7.43
20
7.64
10 7.73
0 .25 .5 .75 1 1.25 1.5 1.75 2
Figure 27. Elongation at Break for Amlon® D Fiber

by Diameter and Speed Draw Ratio.
a) No shroud. Draw is a ratio of initial to final fiber diameter.

b) Shroud at 145ºC. Draw is a ratio of initial to final fiber diameter.
Melt Extrusion 118
80
70
Average Total
60
Elongation (%) 50 5.31
5.35
40
5.94
30 5.99
6.3
20 6.36
6.38
10
0 .5 1 1.5 2 2.5 3 6.54
Draw Ratio, by Speed 6.57
6.75
6.78
8
6.9
6.95
80
6.96
70 7.16
7.2
60 7.23
Elongation (%)
7.24
50
7.32
40 7.37
7.39
30 7.43
20 7.64
7.73
10
0 .5 1 1.5 2 2.5 3
Figure 27. Elongation at Break by Draw Ratio. (continued)
c) No shroud. Draw is a ratio of final to initial roller speeds.

d) Shroud at 145ºC. Draw is a ratio of final to initial roller speeds.
Melt Extrusion 119
7.2.4 Wide Angle X-ray Diffraction
7.2.4.1 Background
The anomalous nature of PAN homo- and co-polymers yields structures
that are dependent primarily upon preparation and processing and secondarily
upon the presence of any comonomer and its concentration. In nearly all wide
angle x-ray diffraction (WAXS) studies and even in cases where single crystals
were examined, the off-equatorial reflections or meridional scatterings are diffuse
at best. Correspondingly, Miller indices are often reported as hk0. As a result,
structural order is thought to be two dimensional. Based on WAXS, various
models of phase structure have been proposed [118], with the strongest
evidence suggesting a single phase [57] or combination of paracrystalline and
amorphous phases [119, 120].
Most analyses of WAXS diffraction patterns show a narrow peak at
2θ≈17º, a broad peak at 2θ≈27º and a small narrow peak at 2θ≈30º. The most
recent and refined [58] protocol for characterizing the degree of paracrystallinity
and amorphousness was developed by Gupta and Singhal [121]. The 2θ≈17º
peak was assigned paracrystalline, the 2θ≈27º peak amorphous and 2θ≈30º
paracrystalline. Based on the interplanar spacing and associated Miller indices,
In the Polymer Handbook [55], three crystalline unit cells are reported for PAN:
hexagonal, orthorhombic and tetragonal, corresponding to syndio- or iso-tactic
stereoregularity. Based on calculated and observed densities, the evidence that
Melt Extrusion 120
supports an orthorhombic unit cell, albeit a quasi-hexagonal form, depending on
the ratio of a and b axes, is more substantiated [65, 122-125].
Numerous attempts have been made to correlate stereoregularity with
structure but inconclusive evidence persists [65, 122-125]. The conformations
and structures appear to be dependent upon preparation and processing in
manners that are dissimilar to other semi-crystalline polymers. Most semi-
crystalline fiber forming polymers are understood in terms of discrete
stereoregularities such as atactic, isotactic or syndiotactic and their distinctive
packings. However, PAN has been shown to exhibit constant paracrystallinity
regardless of tacticity [62]. In 1961, Bohn, et al., suggested in a study of laterally
ordered polymers (polyacrylonitrile and poly(vinyl trifluoroacetate) that for PAN
the severity of the acrylonitrile dipole moments would render an irregular packing
even for a stereoregular PAN [57]. Yet, current studies continue to attempt to
relate properties with types of stereoregularity used to describe semi-crystalline
polymers [59-61]. However, efforts to classify structures in such a way may over-
simply and inaccurately describe the irregular conformations in solid state.
The chains for a PAN homo- or co-polymer are considered to conform in a
helical fashion [57, 126] that pack in rigid rods [127] of 6Å in diameter [57, 128]
having hexagonal or orthorhombic forms [125]. The pitch of the helix is
dependent upon the conformation of the acrylonitrile sidegroups [57]. From
powdered samples, Grobelny, et al., suggest that the degree of amorphousness
and paracrystallinity is not related to stereoregularity, but to a higher degree of
‘perfection.’ Perfection, in this case, is correlated to the smallest full-width at
Melt Extrusion 121
half-max (FWHM) measurements of the 2θ≈17º peak and larger paracrystallinity
coefficients as defined by Hinrichsen [129]. The more perfect structure is
suggested to prefer configurations [118]. In addition to tacticity, annealing was
shown to increase the paracrystalline perfection.
Inclusion of comonomers into the paracrystalline domain tends to reduce
the diameter of the PAN rods, but not necessarily their packing [130, 131]. Due
to an increase of chain flexibility from the absence of such strong dipole
moments in the comonomer, its presence depresses the glass transition
temperature, creates a lower helix pitch and prevents neighboring acrylonitrile
sidegroups from interacting. In so doing, the presence of comonomers lowers
the degree of perfection of the paracrystalline lattice. Yet depending on
temperature and time of annealing, perfection and narrowness of FWHM in
acrylonitrile copolymers can surpass that of the PAN homopolymer. The
rotational flexibility of the comonomer sidegroups further contributes to this
perfection as it facilitates more optimal pairing of acrylonitrile sidegroups [130].
7.2.4.2 Results and Discussion
Overall, the wide angle x-ray reflection spectra (Figure 28) and
transmission patterns (Figure 29) are relatively similar regardless of the
difference in total effective draw ratio. As the fibers with the heat shroud
imparted the highest tenacities, these were chosen for WAXS analysis. The
reflection spectra are consistent with those reported in the literature. A
Melt Extrusion 122
pronounced peak is observed at 2θ≈17º, a broad peak between 2θ angles of 25
and 29º and a third peak between 2θ angles of 29 to 30º. A new peak was
observed at 2θ≈32º for fibers with total effective draw ratios of 5.31 and 7.73,
which may show more distant reflections consistent with those found in highly
drawn fibers [126]. Interplanar d-spacing are also consistent with crystal studies
of homo- and co-polymer PANs. Additional scans will be needed to confirm this
peak and the paracrystal dimensions.
The degree of order or paracrystallinity was calculated based on the
technique described by Gupta and Singhal [121]. The degree of order is similar
to solution processed fiber heat treated at 110 and 150º in the same study. The
similarity of the degrees of paracrystallinity for the fibers prevents full conclusions
from being drawn. The mechanics of the helix deformation during drawing and
its effect on pairing of acrylonitrile sidegroups would likely affect these values. A
more detailed study of fiber x-ray diffraction and more precise control of peak
fitting should enable more precision in this calculation.
The FWHM of the 2θ≈17º peak suggest trends based on method of draw
and the total effective draw ratio. Grobelny found that the FWHM decreased with
paracrystals perfection. Comparing fibers with only spin draw ratio, the fiber with
total effective draw ratio of 7.73 shows a lower FWHM than the fiber with total
effective draw ratio of 5.31. Fibers drawn between the heated draw ratios
showed broader 2θ≈17º peaks. The values of which decreased with larger draw
ratio. More consistent values of FWHM for the 2θ≈27º and 2θ≈30º peaks will
Melt Extrusion 123
enable a discussion of the perfection of the paracrystals and degree of order
imparted through drawing.
The WAXS transmission patterns (Figure 29) show a more ordered
structure by virtue of the intensity of the equatorial reflections. Most patterns of
PAN fibers show more diffuse halos even for drawn fibers. In the case of the
Amlon® D fibers, some evidence of a halo is shown for the total draw ratio of
5.31. However, higher draw ratios show more defined equatorial reflections with
little diffuse meridional scattering. Similar to Colvin and Storr, with higher draw
Table 11. Wide Angle X-Ray Diffraction Reflection Spectrum Analysis of

Amlon® D Fibers
Para-
2 Theta d-spacing Area FWHM
Fiber crystallinity
(º) (Å) (%)
(%)
100 m·min-1 Wind 17.40 5.10 52.74 1.03
100 m·min-1 Draw 25.13 3.54 45.86 54.14 7.97
Total Draw Ratio = 5.31 29.85 2.99 1.40 0.92
400 m·min-1 Wind 14.43 5.08 59.55 1.49
400 m·min-1 Draw 25.66 3.47 37.19 62.81 7.87
Total Draw Ratio = 6.95 28.80 3.10 3.26 0.71
100 m·min-1 Wind 17.52 5.06 49.93 1.42
400 m·min-1 Draw 28.86 3.32 40.07 59.93 4.87
Total Draw Ratio = 7.23 30.37 2.94 10.00 0.88
700 m·min-1 Wind 17.32 5.12 52.75 0.92
700 m·min-1 Draw 27.42 3.25 42.32 57.68 8.29
Total Draw Ratio = 7.73 30.37 2.94 4.93 4.76
ratios through staged and steam drawing, a more 3-dimensional ordering may be
possible [126]. Since the historical method for calculation of paracrystallinity for
solution processed acrylic fibers is based on more diffuse meridional scattering, a
new method for melt processed acrylic fiber may be required.
In general, the plastic deformation made possible in this melt processable
high acrylonitrile copolymer may offer additional opportunities for optimization of
morphology and structure than observed in solution processed acrylic fibers.
Melt Extrusion 124
The relationship between the mechanics of chain deformation, dynamics of
intermolecular sidegroup interactions, perfection of the paracrystalline domains
and optimization of the mechanical properties can be studied both
computationally and empirically.
F5.31 Total Draw Ratio

Count
10 15 20 25 30 35
2 Theta
Figure 28. Wide Angle X-Ray Diffraction Reflection Spectrum for Fibers
Extruded with a Heat Shroud.
Melt Extrusion 125
Figure 29. Wide Angle X-Ray Diffraction Transmission Patterns for Fibers
Extruded with a Heat Shroud
a) 100 m·min-1 Wind, 100 m·min-1 Draw

b) 400 m·min-1 Wind, 400 m·min-1 Draw
Melt Extrusion 126
Figure 29. Wide Angle X-Ray Diffraction Transmission Patterns.

(continued)
c) 100 m·min-1 Wind, 400 m·min-1 Draw

d) 700 m·min-1 Wind, 700 m·min-1 Draw
Melt Extrusion 127
7.2.5 Paracrystallinity
Regardless of whether a single paracrystalline domain pervades the
structure or a combination of amorphous and paracrystalline domain exist, the
enthalpy of ‘recrystallization’ or re-ordering in Amlon® D may be used to support
speculation about the effects of draw on sidegroup interactions. Observations by
Grobelny, et al. and others [118, 121, 130], suggested that the inclusion of
comonomers and processing affects the chain conformation and perfection of the
paracrystalline domain through its effects on optimal intrermolecular acrylonitrile
pairing. While the details of local segmental deformation and pairing are beyond
the scope of a macroscopic analytical technique like DSC, it is nevertheless a
useful tool to discuss how may be optimized through the chain conformation.
The degree of reordering, which hereon will be referred to as the degree
of paracrystallinity, is presented as a function of total effective draw ratio in Table
12 and Figure 30. More significant changes in enthalpy are shown for fibers
having a higher draw ratio and lower spin draw ratio. For the fibers extruded
without the shroud, the paracrystallinity reaches an optimum value, with the
highest total draw ratio imparted through draw between heated rollers, not
through spin draw, Figure 30b and 30c. The value of the optimum is the same as
that of the fiber extruded with the shroud at the same windup speed. Rather than
reaching an optimum, these fibers consistently exhibited a lower degree of
paracrystallinity with higher draw ratio. The fiber spun without the shroud at the
highest draw ratio showed an enthalpy similar to that given by the highest drawn
fiber extruded with the shroud. A similar trend is observed with fibers wound at
Melt Extrusion 128
200 m·min-1 with a shroud, Figure 30c. For fibers drawn with a shroud at 400
m·min-1 or more marginal changes in the enthalpy are observed. In general,
however, it is observed that enthalpy increases with draw, regardless of whether
it is spin draw or draw ratio. When comparing fibers with the same winding roll
speed, the highest draw ratios showed a decrease in the enthalpy.
Differences in enthalpy may be related to changes in intermolecular
bonding as affected by the amount of draw and rotational flexibility of
comonomer.
Table 12. Differential Scanning Calorimetry Data for Amlon® D Fiber

Winding Drawing Mean First First Second Second
Shroud
Roll Roll Total Reorder Reorder Reorder Reorder
Temperature
Speed Speed Draw Peak Enthalpy Peak Enthalpy
( ºC )
( m·s-1 ) ( m·s-1 ) Ratio ( ºC ) ( J/g ) ( ºC ) ( J/g )
0 100 100 5.35 162.25 8.356 162.05 8.331
0 100 200 5.99 161.89 8.589 161.41 8.649
0 100 300 6.38 163.83 9.082 163.54 8.996
0 100 400 6.54 161.93 7.466 161.85 7.742
145 100 100 5.31 179.57 9.235 179.67 9.093
145 100 200 6.30 177.19 8.427 177.23 8.356
145 100 300 6.75 178.65 7.867 179.75 7.755
145 100 400 7.23 161.44 7.451 161.05 7.424
145 200 200 5.94 171.39 7.604 178.06 7.816
145 200 300 6.57 164.26 8.747 164.20 8.594
145 200 400 6.78 163.36 8.506 163.01 8.561
145 200 500 6.90 179.68 9.689 180.21 9.254
145 200 600 7.64 162.80 8.143 162.94 8.150
145 300 300 6.36 167.37 8.796 167.74 8.826
145 300 400 7.16 163.90 8.887 163.84 8.816
145 300 500 7.39 169.92 9.433 172.01 9.515
145 400 400 6.95 160.40 8.219 160.64 8.294
145 400 500 6.96 162.67 8.564 162.44 8.564
145 400 600 7.24 163.71 8.928 163.52 9.016
145 500 500 7.20 163.83 8.824 163.80 8.841
145 500 600 7.32 169.99 9.094 170.45 9.108
145 600 600 7.37 177.33 8.075 179.38 8.258
145 600 700 7.43 176.78 8.498 176.78 8.723
145 700 700 7.73 165.73 9.471 165.78 9.379
Melt Extrusion 129
10
9.5
Total Effective
Draw Ratio
9
Enthalpy (J/g)
5.31
8.5 5.35
5.94
8 5.99
6.3
7.5 6.36
6.38
7 6.54
5 5.5 6 6.5 7 7.5 8 6.57
6.78
6.9
10 6.95
6.96
9.5 7.16
7.2
9
Enthalpy (J/g)
7.23
7.24
8.5
7.32
7.37
8
7.39
7.43
7.5
7.64
7.73
7
5 5.5 6 6.5 7 7.5 8
Figure 30. Second Cooling Enthalpies for Amlon® D Fiber

by Total Effective Draw Ratio.
a) For all fibers by average total effective draw ratio

b) No shroud. Windup Speed is 100 m·min-1.
Melt Extrusion 130
10
9.5
Total Effective
9 Draw Ratio
Enthalpy (J/g)
5.31
8.5 5.35
5.94
8 5.99
6.3
7.5 6.36
6.38
7 6.54
5 5.5 6 6.5 7 7.5 8
6.57
6.78
6.9
10 6.95
6.96
9.5
7.16
7.2
9
Enthalpy (J/g)
7.23
7.24
8.5
7.32
7.37
8
7.39
7.5 7.43
7.64
7 7.73
5 5.5 6 6.5 7 7.5 8
Figure 30. Second Cooling Enthalpies by Draw Ratio. (continued)
c) Shroud at 145ºC. Windup Speed is 100 m·min-1.

d) Shroud at 145ºC. Windup Speed is 200 m·min-1.
Melt Extrusion 131
7.2.6 Conclusions
Properties of Amlon® D fibers even though not yet optimized still show a
tenacity similar to that found in Dralon®. The tenacity of the Amlon® D fiber with
higher draw ratios should therefore be commercially acceptable. Smaller denier
fibers are currently being attempted through modification of the orientation zone
by incorporating a temperature device and drawing at different temperatures
[132].
Evidence of the possibility of additional property optimization beyond that
which is observed in solution processed acrylics is illustrated in wide angle x-ray
diffraction spectrum. Melt processability creates a structure that is able to
undergo chain deformation that affects intermolecular bonding, paracrystallinity
and the degree of perfection of the paracrystalline domain. Studies of fibers
drawn to higher ratios through staged and steam drawing as well as annealing
could further enhance the mechanical properties.
General Conclusions 132
8 General Conclusions
This study presented fundamental economical, technical and scientific
aspects of one version of the first innately thermoplastic and melt-processable
high polyacrylonitrile, Amlon® D. The following conclusions can be drawn from
those presented in corresponding sections of the thesis:
• The economic analysis presented shows that because of the low raw
material cost Amlon® will undoubtedly find increased consumption in the
world market. Mechanical property optimization due to melt processability
and intrinsic UV and chemical resistances will enable new applications.
• The intermediate length of acrylonitrile sidegroups is long enough for
mechanical integrity and dimensional stability while short enough to
become melt-processable. ‘Melting’ or de-coupling of sidegroups occurs
as a function of time and temperature. Cooling exhibits ‘recrystallization’
exotherms which can be considered sidegroup re-coupling.
• The rheological study shows that the behavior of molten polymer flow
varies little over a wide range of melt temperatures and times. Of the
processing parameters studied, the ideal temperature for melt processing
was found to be is 220ºC and melt time was found to be 5 minutes.
• Tenacity of Amlon® D fibers were on average higher than a commercial
solution spun fiber. Some extrusion conditions created fibers with
tenacities similar to most commercial poly(ethylene terephthalate) and
polyamides and one condition produced higher tenacities.
General Conclusions 133
8.1 Future Work
The science and engineering of melt extrusion of fibers is well developed.
As the basic thermodynamic and rheological properties of one type of Amlon®,
Amlon® D, are now established, optimization of fiber properties can now be
pursued. In particular, staged drawing, steam drawing and annealing
consistently improve fiber properties. High speed spinning may possibly further
enhance orientation and properties.
The Amlon® technology enables the synthesis of a range of resins
depending on comonomer, polymer structure and molecular weight. A
thermoplastic high polyacrylonitrile polymer has been an object of desire for
decades. Much of the longstanding mystery concerning the crystal morphology
of PAN is fortified by the lack of understanding their processability vis-à-vis
commodity thermoplastics. While this work has served to offer new knowledge
concerning the science of the polymer, much about this anomalous and
prodigious material remains to be understood. The ability to structure
acrylonitrile copolymers will create many opportunities to explore other
theoretical polymer science ramifications and to design polymers for specific
applications. Computational modeling will likely offer significant insight via the
speedy investigation of new polymers and the physical mechanisms that enable
enhanced properties. In general, as manufacturing technology progresses to the
point of precisely controlling the arrangement of matter and molecules, the
consequences of the structure-property relationship will continue to offer unique
insights into Nature, in all its breathtaking and inspiring forms.
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ABSTRACT

HUTCHINSON, SHAWN ROBERT. Thermoplastic polyacrylonitrile: investigation

W. OXENHAM, B.S. GUPTA and A.E. TONELLI).

The objective of this research is to understand the structure, melt

behavior, and fiber properties of Amlon® D, part of a family of thermoplastic high

acrylonitrile (PAN) copolymer resins. A proposed crystal morphology model

based on predicted and observed comonomer sequence lengths and melting

behavior is presented. Thermograms of basic melt behavior demonstrate there

is melting, but surprisingly no evidence of a first-order phase transition is

Time-temperature stability and flow behavior was used to gain an

understanding of processing parameters. Thermogravimetric analysis with mass

Monofilaments were extruded using a single bore device with a range of

polymer is characterized and correlated with the mechanical properties using

wide angle x-ray diffraction and differential scanning calorimetry analyses.

SHAWN ROBERT HUTCHINSON

A thesis submitted to the Graduate Faculty of

North Carolina State University

In partial fulfillment of the

Requirements for the degree of

This work is dedicated to

whose support made with work possible.

THE ROAD NOT TAKEN

TWO roads diverged in a yellow wood,

And sorry I could not travel both

And be one traveler, long I stood

And looked down one as far as I could

To where it bent in the undergrowth; 5

Then took the other, as just as fair,

And having perhaps the better claim,

Because it was grassy and wanted wear;

Though as for that the passing there

Had worn them really about the same, 10

And both that morning equally lay

In leaves no step had trodden black.

Oh, I kept the first for another day!

Yet knowing how way leads on to way,

I doubted if I should ever come back. 15

I shall be telling this with a sigh

Somewhere ages and ages hence:

Two roads diverged in a wood, and I—

I took the one less traveled by,

And that has made all the difference. 20

Shawn Robert Hutchinson was born on February 2, 1978 in Frankfurt am

towering gardens. In 1996, he graduated from Fuquay-Varina Senior High

worked as a software developer with a dotcom in Washington, D.C. and New

Seeking to fulfill questions about the nature of existence, he sought an

experiential worship that was rediscovered in creativity – ultimately finding

Vedanta and Santhana Dharma as a profound system of self-knowledge. After a

to graduate school at North Carolina State University to complete the

development of a new fabric. Unbeknownst to him lie waiting the world of

an aspiring scientist. Appreciation is also extended to members Drs. J.P.

of the Institute of Textile Technology provided enduring encouragement and

recommendations along the journey.

Sankar of the Chemistry Department at North Carolina State University provided

nuclear magnetic resonance training. Tulane University, Drs. D. De Kee, Y.

Science (TIMES) graciously allowed their equipment to be used for the

rheometry and part of the thermogravimetric analysis work. Thanks to Dralon,

This work was sponsored by the Master’s Graduate Fellowship Research

member companies is greatly appreciated.

4 MARKETS AND POTENTIAL .........................................................................30

Table 2. Comparative Properties of Synthetic Fibers..........................................49

Table 3. Comonomer Distributions and Number Average Sequence Lengths for